l19Sn-NMR Parameters

BERND WRACKMEYER
Institut fur Anorganische Chemie der Universitat Munchen,
Meiserstrasse I , 0-8000 Munchen 2, Federal Republic of Germany

I. Introduction. . . . . . . . . . . . . . . 73
11. Experimental . . . . . . . . . . . . . . . 74
A. Referencing . . . . . . . . . . . . . . 75
B. 'H{'"Sn} Heteronuclear double resonance . . . . . . . 75
C. Direct observation of 'I9Sn resonances by pulse Fourier transform (PFT)
NMR . . . . . . . . . . . . . . . 76
111. Nuclear spin relaxation . . . . . . . . . . . . 80
A. General . . . . . . . . . . . . . . . 80
B. Relaxation mechanisms . . . . . . . . . . . 81
IV. Chemical shifts, ~ 5 " ~ S n . . . . . . . . . . . . 84
A. General . . . . . . . . . . . . . . . 84
B. Patterns of '"Sn chemical shifts. . . . . . . . . . 85
C. Correlations between 'I9Sn chemical shifts and other Group IV element
chemical shifts . . . . . . . . . . . . . 108
V. Indirect nuclear spin-spin couplings, nJ(1'9SnX) . . . . . . . 109
A. General . . . . . . . . . . . . . . . 109
B. Patterns of couplings, "J(SnX) . . . . . . . . . . 110
VI. Conclusions . . . . . . . . . . . . . . . 159
Acknowledgments . . . . . . . . . . . . . . 161
References . . . . . . . . . . . . . . . . 177

I. INTRODUCTION

In the past three decades the chemistry of tin compounds has gained
considerable importance both in basic research and in industrial applications.
There are so many interesting aspects of inorganic and organic tin chemistry
that the need for a convenient analytical tool is clearly indicated. This can be
filled by tin NMR spectroscopy since there are three magnetically active
( I = 4) tin isotopes ("'Sn, "'Sn , l19Sn) (Table 1). Most tin NMR param-
eters refer to the Il9Sn nucleus owing to its properties (Table 1) (although
there is no problem in observing "'Sn resonances); the low natural abun-
dance makes the measurement of "Sn resonances unfavourable.
Multinuclear facilities, which became available with pulse Fourier trans-
form (PFT) NMR spectrometers in the last 5-6 years, have stimulated much
work in the area of l19Sn NMR. Therefore, the present review is intended to
73

Copyright 8 1985 by Acadcmic Pras Inc. (London) Ltd.

ANNUAL REPORTS ON NMR SPECTROSCOPY All right$of reproduction in any form rcscrvcd.
VOLUME 16 ISBN 0-12-M53169
 74 BEXND WRACKMEYER

TABLE I
N M R properties of tin isotopes
~~~ ~

Natural Magnetic Magnetogyric NMR Relative

abundance moment ratio y frequency" receptivityb
Isotope ("/.I (p/pN) (lo7 rad T-' sec-') (g,Hz) (Dp,D')
1'5Sn 0.35 - 1.582 -8.7475 - 1.22 x 10-4,0.7
1'7Sn 7.61 - I .723 -9.530 35632295 3.44 x 19.5
'19Sn 8.58 - 1.803 -9.971 37290665 4.44 x 25.2
~ ~~ ~~~ ~ ~~~

Neat (CH,),Sn, for various solventsLo

Relative to 'H(Dp), relative to "C(DC).See R. K. Harris in N M R and the Periodic Table (R.K.
Harris and B. E. Mann, eds), Academic Press, London, 1978, p. 4.

serve several purposes: (1) the compilation of 'I9Sn chemical shifts (a1l9Sn)
from previous reviews on organotin compound^'^ and inorganic tin
corn pound^^*^*^ is updated (literature covered up to the end of 1983);
(2) indirect nuclear spin-spin couplings, "J('I9SnX) (n 2 I), are reviewed
although no complete survey can be given since there are too many data
available [e.g., J(1'9Sn1H) or J(1'9Sn'3C)]; (3) relaxation mechanisms
concerning the 9Sn nucleus are discussed briefly; and (4) experimental
details for 'I9Sn-NMR measurements are given.
Most of the references can be found in the tables for 'I9Sn chemical shifts.
For organotin compounds many references that contain the 6119Sndata very
often list 'H- and I3C-NMR parameters too, including the couplings
"J("9Sn1H) or "J("9Sn'3C). The discussion in the text does not aim for
completeness but is necessarily restricted to those aspects that the author
believes to be of particular significance. There are, however, so many exciting
developments in the field of tin chemistry that have been explored using
lI9Sn-NMR parameters that an unbiased selection is difficult to achieve.

11. EXPERIMENTAL

The observation of "'Sn resonances can be achieved either by hetero-

nuclear double resonance, e.g., 'H{ 119Sn},6.7or by direct observation.
Although the latter approach, in principle, presents no difficulty with modern
PFT NMR spectrometers there are still a number of useful applications
for heteronuclear double resonance experiments. Continuous wave (CW)
methods for the direct observation of lI9Sn resonances are of limited
value owing to the relatively low receptivity DP (relative to 'H NMR) of
4.44 x for the II9Sn nucleus (Table 1).
 ''9Sn-NMR PARAMETERS 75

A. Referencing
In view of the difficulties encountered for heavy nuclei by using a particular
compound as an internal (chemical reactions, solvent effects) or external
reference (bulk susceptibility corrections), it appears preferable to use a
known absolute frequency Z(119Sn)8-'0 as reference (Table 1). This is a
straightforward procedure for PFT N M R spectrometers. In heteronuclear
double resonance experiments (e.g., 'H{' "Sn}) this is the method of choice in
most cases anyhow. For most purposes it seems that corrections for different
bulk susceptibilities are unnecessary. All 6' 19Sn data in the tables given here,
and in general in the literature too, are referred to (CH,),Sn, a positive sign
denoting lower shielding or a shift to higher frequencies (lower field).
Depending on the referencing procedure, differences for the reported 'Sn ''
chemical shifts of up to several ppm may be found even for identical
compounds studied under comparable conditions.

B. 'H{' 19Sn} Heteronuclear double resonance

The techniques for 'H{' I9Sn} heteronuclear double-resonance experi-
ments have been re~iewed.~.'In CW 'H-NMR spectra, a '19Sn satellite,
'
arising from 19Sn-'H spin-spin coupling, is monitored while the irradiation
'
frequency field B, for the 19Sn nucleus is swept through the range expected
'
for the 19Snresonance in question. Provided that the power adjustment of B,
'
is correct, the maximum effect on the ''Sn satellite corresponds accurately to
'
the centre of the related 19Sn resonance.
In PFT mode several 'H-NMR spectra are recorded, each with a different
' '9Sn irradiation frequency and otherwise unchanged parameters. By com-
parison of the absolute intensity of the '19Sn satellites, or by subtraction of
the undistorted from the distorted spectra, the relevant information can be
obtained. It is obvious that a series of these experiments may be particularly
helpful in studying reaction mixtures by correlating the 'H-NMR signals with
the various '19Sn resonances. The latter are in general very useful for
structural assignments. As shown later, this type of experiment is the one-
dimensional equivalent of the two-dimensional (2D) heteronuclear shift
correlated spectra" that can be obtained with modern spectrometers, vide
infra. Experiments with 'H{' "Sn} are always very useful when it is difficult to
measure the '19Sn resonance directly, even with modern equipment. This
applies when the '19Sn resonance is very broad (e.g., in the case of partially
relaxed scalar coupling between '19Sn and a quadrupolar nucleus-such as
"B-or in cases of chemical exchange) while the 'H resonances are not
significantly affected.' ,-'
However, the accurate measurement of the line
width of the Il9Sn resonances in the internuclear double resonance (INDOR)
'
mode requires a careful setting of the power of the 19Snirradiating field, B,
76 BERND WRACKMEYER

so as to observe the condition [(rl 19,,B2)/2n] 2 A v (A v is the breadth of the

perturbed line). Frequently, this is difficult to achieve, in particular when the
'19Sn nucleus is coupled to several different protons with differing
nJ(l19Sn'H) couplings.
In addition to the determination of the '19Sn chemical shifts (~5"~Sn)the
'H{ 'I9Sn} experiments can be used in either mode, continuous wave or pulse
Fourier transform, to determine relative signs of indirect nuclear spin-spin
The absolute signs of a great number of nJ(119Sn'H)values are
known, which allows the absolute sign of other J('I9SnX) couplings to be
determined using the appropriate 'H{ "'Sn} double resonance experiment.
Of course, one can think of other heteronuclear double resonance
experiments, e.g., '9F{"9Sn} or 31P{'19Sn}, which will be useful in dealing
with special problems.

C. Direct observation of lI9Sn resonances by pulse Fourier

transform (PFQ NMR
For most applications, '19Sn PFT NMR is the preferred alternative to
heteronuclear double resonance 'H{' 19Sn},particularly, when modern NMR
spectrometers with multinuclear equipment are available. This is readily seen
by looking at the values for the receptivity D" ('I9Sn) in Table 1. The only
drawback in the nuclear magnetic properties (always in comparison with 13C
NMR) is the negative sign of the magnetogyric ratio y119,,. Therefore, a
significant contribution from Sn-H dipole-dipole interactions in organotin
compounds to the relaxation of the '19Sn nucleus causes a negative nuclear
Overhauser effect (NOE) which may lead to a serious loss of signal intensity in
'
normal 'H broadband decoupled 19Sn-NMR spectra (119Sn{'H}) (Fig. 1).
Therefore, it is important (1) to consider the relative importance of the various
relaxation mechanisms (Section 111) and (2) to select suitable techniques for
recording '19Sn{'H} spectra (e.g., gated decoupling of 'H in order to
suppress the NOE as shown in Fig. 1, spin-polarization transfer techniques,
vide infra).
It appears that in most organotin and inorganic tin compounds, under
normal conditions, the longitudinal relaxation times Tl are of the order of a
few seconds. This enables one either to use fairly large pulse angles [the
optimum pulse angle a corresponds to the relationship cos a = exp[ - (AT -F
PD)]/T,, where AT is the acquisition time, PD is the pulse delay or
relaxation delay tirne]l6 in normal '19Sn{'H} spectra without pulse delay
times or to use fairly short delay times (ca. 2 5 x Tl) and 90" pulses in NOE-
'
suppressed 19Sn{'H} spectra.
In addition to circumventing the negative NOE the various polarization
transfer (FT) techniques, e.g., insensitive nuclei enhanced by polari-
 "'Sn-NMR PARAMETERS 77

PW 1Ws AT 1.0s
(90")
16 Scans

(1)
BunjSn, Et
,c=c:
Bun3Sn BEt,
0)
'leSnfH] Pulse delay 25 s

0)

(1)

3(19Sn6X6 -551 - 74.3

119
Sn p H inverse gated} Dday 25s

FIG. 1 . lI9Sn-NMRspectra at 74.63 MHz of the reaction mixture Bu",Sn-C=C-SnBu",

and Et, B in CDCl, (20% v/v) at 28°C. (a) 119Sn{'H}-NMR spectrum, parameters as
shown. (b) NOE suppressed, parameters same as in (a). The broader lL9Snresonance of
Bun&-CEC-SnBu", in (a) as compared to @) is the result of a tempkrature gradient
6'19Sn/K caused by the 'H decoupler.

zation transfer and distortionless enhancement by polarization transfer

(INEPT, DEPT),"-" offer additional advantages for the measurement of
"'Sn resonances of organotin compounds. The optimum enhancement
factor, EOp1," of the intensity of the 'H decoupled "'Sn resonance signal
depends upon the number of protons coupled to "'Sn with identical
"J("'Sn'H) couplings (e.g., for six protons, E,,, = IyIH/yl 19sm1 1.55 = 4.16).
It is important to note that the repetition time of the pulse sequence is now
governed by the relaxation time, T 1 ,of the protons, which may be shorter
than T,("'Sn). There are numerous nJ("gSnlH) (n 2 1) data known" and
many of these values can be predicted with reasonable accuracy. Therefore,
the corresponding "'Sn-NMR spectra (either 'H coupled, DEFT,'' or
INEPT+?Opulse sequence preferred, or 'H decoupled) are readily obtained. It
should be noted that the relaxation behaviours of the 'H and the "'Sn nuclei
must be considered. In some cases the transverse relaxation times T,("'Sn)
are relatively short for various reasons (vide infru). Therefore, it is important
to select the PT techniques with respect to the behaviour of the transverse
magnetization of the "'Sn nucleus. If T2is relatively short, which is true
for many organotin halides, the INEPT pulse sequence (refocused INEPT for
78 BERND WRACKMEYER

'H decoupled spectra) gives a better SINratio than the DEPT pulse sequence
since the evolution time for Mx,y in the refocused INEPT experiment is
shorter. Similarly, if T,(119Sn) is shorter than Tl('H) the PT technique fails
to give results. This situation may arise in very high field '19Sn NMR
(B,, > 4.7 T) if chemical shielding anisotropy (CSA) relaxation becomes
dominant.
Although there are no examples in the literature so far, it is expected that
two-dimensional NMR techniques,' like hetero correlated 2D 'H-' I9Sn
NMR, will be extremely helpful in studying complex reaction mixtures of
organotin compounds. This type of experiment yields a 2D spectrum in which
the coupled nuclei (e.g., 'I9Sn and 'H) share a signal with the coordinates of
~ 5 " ~ S and
n 6'H.
The 'I9Sn-NMR spectra in Figs. 2-4 give some idea of the wealth of
information to be gained from direct '19Sn-NMR spectra. Thus, values for
the couplings lJ(l19Sn13C), 1J("gSn77Se), and ZJ("9Sn"7Sn) are readily
obtained (Fig. 2). In particular, zJ(119Sn"7Sn) data [or zJ("9Sn119Sn)] are
of great value for structural assignments (Fig. 3) and, therefore, in the analysis

I I I I I I I I I I I I I
t loo Hz*

-
FIG. 2. '"Sn-NMR spectrum at 74.63 MHz ('H broadband decoupled) of bis-
(trimethylstanny1)selenide (10% C,D, in 10-mm 0.d. tube); time required: 15 minutes.
 e
C
A
I E

I I I I I I I 1 I I I I I I

100 50 "'~n

1 I I I I I I I I I I I

100 50 Ps~
FIG. 3. (a) ' 19Sn-NMR spectrum at 74.63 MHz of a mixture of (Me,SnS), and (Ph,SnS),
(1: I). (b) '"Sn-NMR spectrum at 74.63 MHz of a mixture of (Me,SnSe), and (Me,SnS), (1: 1).

-
Both mixtures 10% in CDC1, in 10-mm 0.d. tubes; 'H inverse gated decoupling for NOE
suppression;time required is (a) 1 hour and (b) -0.3 hour; '17Sn, 'I9Sn, and (b) 77Sesatellite
signals verify the assignment.
80 BERND WRACKMEYER

Se -
n:
se-

se-

100
i 50 0 - !PJ J"&

FIG. 4. "'Sn-NMR spectrum at 74.63 MHz of a mixture (Me,SnSe), + (Ph,SnS), (1: 1) in

I

CDCI, in a 10-mm 0.d. tube, 'H inverse gated decoupling for NOE suppression;time required:
6 hours. Most lI7Sn, *19Sn,and 77Sesatellite signals can be detected and have been used for
assignment purposes.

of mixtures. In general, chemical shifts, 6119Sn,and couplings are excellent

tools in tin chemistry. This is evidenced by Fig. 4, which shows that the
reaction of only two compounds leads to a mixture consisting of 20 different
compounds. This mixture is readily analysed using "Sn-NMR spectroscopy.

111. NUCLEAR SPIN RELAXATION

A. General
In general, numerous intra- and intermolecular interactions contribute to
the values of T, and T 2 .For the purposes of this article, it is appropriate to
consider mainly the influence of relaxation phenomena on experimental
conditions. There are many excellent accounts on nuclear spin relaxation in
the Furthermore, we assume conditions which are referred to
as those of the motional narrowing limit:
wo2702 << 1 (1)
where wo is the resonance angular frequency and 70 is the correlation time to
characterize molecular motions which produce local fluctuating magnetic
 '9Sn-NMR PARAMETERS 81

fields necessary for nuclear spin relaxation. Since T , becomes frequency

independent under these conditions (relatively nonviscous samples), T , = T2
can be assumed in the absence of CSA relaxation or scalar relaxation of the
second kind (vide infra). We may distinguish between three types of
correlation time: (1) the rotational correlation time, zc, (Brownian molecular
motion) increases with molecular size (molecular association) and viscosity
(decreasing temperature); (2) the translational correlation time, which is
similar to z, as far as its dependence on molecular size and temperature is
concerned; (3) the spin-rotation correlation time, zSR,which characterizes the
interaction between the nuclear magnetic moment and the rotational magnetic
moment (spin-rotation interaction). For the following it is important to note
the inverse temperature dependence of z, and zsR since the latter increases
with increasing temperature (or decreasing viscosity):
z,zSR = (Z/6kT) (2)
where Z is the moment of inertia (Hubbard's relation29).

B. Relaxation mechanisms
Contributions to nuclear spin relaxation can arise from intramolecular
magnetic dipole interactions (TIDD,T2DD)(for the present discussion inter-
molecular magnetic dipole interactions will be neglected), from spin-rotation
interactions (TISR,T2SR), from scalar coupling (TlX, T2sc),and from chemical
shielding anisotropy (TlaA, T2aA).Among these, magnetic dipole and spin-
rotation relaxation are of particular importance, at least for many organic
and inorganic tin compounds. Scalar coupling must be considered for the
19Snnucleus linked to quadrupolar nuclei (e.g., C1, Br, I, N, B), whereas CSA
can be of importance at high magnetic field strengths (>4.7 T). According to
Eq. (3), TIDD and, of course, T2DD depend upon the inverse sixth power of the
internuclear separation (in general the 'I9Sn-H distance, rSnH).Therefore, the
magnetic dipole interaction in many organotin compounds will become
increasingly important at low temperature or for molecules or molecular
associates of fairly large size. In any case, one has also to consider the
intramolecular mobility of the organotin molecule which discourages the use
of an effective correlation time T, for the whole molecule (Fig. 5).

The amount of cross-relaxation by intramolecular dipole-dipole coupling

in liquids is determined by the NOE.30 The changes in signal intensity are
readily observed by comparison of the ,19Sn-NMR spectra which have been
obtained by normal broadband 'H decoupling with those obtained by gated
82 BERND WRACKMEYER

8 Scans, AT 1.6 s
PW 16/( s (90')

119
Sr H
: inverse gated}
Delay 25 s

FIG. 5. "'Sn-NMR spectrum at 74.63 MHz of an allene derivative containing two different
types of triethylstannyl groups. NOE values: qMX = - 1.34; q.,,, = -0.33 (1) and -0.82 (2). The
different NOES observed for the "'Sn (1) and "'Sn (2) nuclei are attributed to their different
mobilities. For steric reasons a greater mobility of the Et,Sn (1) group is expected, leading to a
shorter effective correlation time T~ and, consequently, to longer values of TIDD("'Sn).
Therefore, spin-rotation relaxation is believed to be the more effective mechanism for "'Sn (1).
with respect to "'Sn (2). (a) Normal 'H broadband decoupled "'Sn-NMR spectrum. (b) NOE-
suppressed 'H broadband decoupled "'Sn-NMR spectrum.

'H decoupling leading to suppression of the NOE (Figs. 1,5). The maximum
NOE, in the extreme narrowing limit, corresponds to
'
Vrnax(' 9Sn) = o % I , / h 19~~) (4)
which gives qrnax(1'9Sn)= - 1.34, leading to an inverted '19Sn resonance
signal with 34% of the intensity of the '19Sn resonance recorded with NOE
suppression. Therefore, owing to the negative sign of y119sn the intensity of
the '"Sn resonance in "9Sn{ 'H} experiments varies between + 1 and -0.34,
depending upon the relative contribution of Sn-H magnetic dipole relaxation
in comparison with the other relaxation mechanisms.
l - ~ ~ 2) clearly support the
Experimental T1(1'9Sn) data a ~ a i l a b l e ~ (Table
proposal of competition between magnetic dipole and spin-rotation inter-
 TABLE 2
Longitudinal relaxation timea T,('I9Sn).

Field
Tl ( 19Sn)b T,DD T," Molecular T strength
Compound (seconds) (seconds) NOE' (seconds) Solvent weight (K) (TI
Pr",Sn 4.76 17.24 -0.37 6.67 Neat 29 1 307 2.1 1
Bun,% 6.29 9.80 -0.86 17.54 Neat 347 307 2.11
Pr", SnCl 4.78 22.73 -0.28 6.06 Neat 283 307 2.11
Bu",SnCI 5.81 11.49 -0.68 1 1.76 Neat 326 307 2.11
Bu",SnH 4.65 14.49 - 0.43 6.85 Neat 29 1 307 2.11
(Bu",Sn),O 6.55 13.33 -0.66 12.82 Toluene/ 50YO 596 298 2.35
Ph,SnH 1.51 1.67 -1.21 15.63 Toluene/ 50YO 351 303 2.11
From reference 37.
+
(I

I/T,('19Sn) = (I/TIDD) (l/TISR).

Observed NOE; qmar= - 1.34 for llgSn{lH}.
84 BERND WRACKMEYER

actions. Considering the inverse relationship of the correlation times, which

describe the time dependence of the fluctuating magnetic field created by the
tumbling of the molecule in solution (z,) and the energy exchange between
the nuclear spin and the rotational magnetic moment of the molecule (zSR),
the dominance of one or the other mechanism is readily evident from the
following measurements: (1) determination of the NOE (Figs. 1, 5); and
(2) temperature dependence of T,(I19Sn), which also indicates whether
another mechanism (T1%, TICSA) may be operating.
It has been shown that scalar interactions and CSA ('19Sn NMR at 2.07 and
2.3 T) are insignificant mechanisms for the longitudinal relaxation of the
I19Sn nucleus. However, CSA might be expected to become important at
'
higher field strengths (> 4.7 T) for the 19Sn nucleus in molecules with lower
than cubic symmetry, as has been found for the '07Pb nucleus.38 Since CSA
relaxation appears to be of minor importance37for Bo < 4.7 T and TlaA =
1.17T2CSA(in the motional narrowing limit), significant contributions to
the line width of '19Sn resonances can be expected only from scalar coupling
contributions due to scalar relaxation of the second kind.24From ( 5 ) and (6)
it follows that significant broadening of II9Sn resonances may be expected
when the I19Sn nucleus is coupled to a quadrupolar nucleus X (see Fig. 9,
Section V,B,3,c).
'19Sn)]-'
W1,2(1'9Sn)= [7cT2( (5)
(for Lorentzian line shape and negligible inhomogeneity the full width at half
height is given by Wl,2)
[T2SC(119Sn)]-1 +
= +n2[~(snx)]2Sx(Sx I)T,(X) (6)
[TlSC(1'9Sn)has been neglected, S, refers to the nuclear spin of XI.
The linewidth in Eq. ( 5 ) results from the I19Sn-NMR spectrum, and the
value of Tl(X) for the quadrupolar nucleus X can readily be obtained from
the X-NMR spectra. Thus, the value of J(SnX) can be estimated from
Eqs. ( 5 ) and (6) if other contributions to T2('19Sn) are small.

IV. CHEMICAL SHIFTS, d1I9Sn

A. General
Following Ramsey's t e r m i n ~ l o g ythe
~ ~nuclear screening a, results from
diamagnetic (ad)and paramagnetic (ap)components:
a =ad + op (7)
In agreement with Ramsey's theory, a d and apare large and of opposite sign,
even for molecules of small or moderate size. Therefore, the calculation of
 "9S~-NMR PARAMETERS 85

reliable values for the nuclear screening of the heavier nuclei has not yet been
realized. Serious errors can be introduced from the choice of the atomic basis
set, since the value of a depends upon the origin chosen.40Among the various
semiempirical appro ache^,^^ Pople's MO treatment of nuclear screening
(independent electron model) circumvents some of these problems and the
screening is given mainly as the sum of diamagnetic and paramagnetic local
and nonlocal contributions.4244 These terms, a?, a?, etc., must not be
confused with the terms in Ramsey's equation. The independent electron
model shows that a is controlled by a p a n d a?. While dd"' is expected to
remain fairly constant for a given nucleus in different
0 = (Od'OC + a?) + (gd"on-loc + aPnon-loc) (8)
surroundings, large changes in the magnitude of a? may result. This ap-
proach is further simplified by using an average excitation energy (AEE =
AE)45 instead of summing over all excitation energies for the excited singlet
states which are mixed with the ground state as the result of the application of
an external magnetic field B, .
This has led to the widely used expression for a? considering np and nd
electrons

where p, is the permeability of free space, pB the Bohr magneton, r the radius
of the np and of the nd orbitals, and P, and D, correspond, respectively, to the
imbalance of the valence np and nd_electronson the atom A.
This model may be applied with some success to screening data for nuclei in
series of closely related compounds and it aids in the qualitative understand-
ing of the physical principles of nuclear shielding. However, it should be made
clear that the discussion of variations in the local paramagnetic term a?(A)
is of limited value owing to the simplifications assumed. Indeed, it appears
that the influence of nearest neighbours (point dipole approximation) is not
properly reflected by a P ( A ) , in particular for heavy atom s u b ~ t i t u e n t s . ~ ' ~ ~

B. Patterns of ' 9Sn chemical shifts

1. Coordination number
Assuming the relevant excitation energies to be fairly constant, the local
paramagnetic term may be said to represent the imbalance of charge.
Therefore, we expect some correlation between a? and local symmetry. This
is evident from the increase in lI9Sn nuclear shielding for compounds in which
the coordination number increases from 2 to 26.5*50-73*365 The significant
 TABLE 3
Orgnnotrimethyltincompounds,' tio coordination number = 4

Compound b119Sn Solvent Footnotes Reference

Me,Sn 0 - -
Me,SnEt +3.0 CCI, 8
+4.2 25% CH,Cl, 254
+ 5.3 C6D6 255
Me,SnPr" -2.3 25% CH,CI, 254
Me, SnPr +8.6 25% CH,CI, 254
+9.8 C6D6 d 102
Me,SnBu" - 1.0 25% CH,Cl, C 254
-0.56 C6D6 e 102
Me,SnBus + 5.3 C6D6 f 102
+ 3.3 C6D6 86
Me,SnBu' + 19.5 CDCI, C 170
Me, Sn-CH, Bu' - 14.2 25% CH,CI, 254
- 14.4 CDCI, 170
Me,Sncyclo-Pr + 14.0 25% CH,CI, 254
Me, Snchex -4.7 25% CH,CI, C 254
1-Me3Sn-2-Ph-chex -9.1 C6D6 101
I-Me&-norbornane (exo) +4.4 25% CH,Cl, 254
+3.3 C6D6 101
I-Me&-norbornane (endo) -0.5 C6D6 101
7-Me3Sn-norbornane -9.2 25% CH,CI, 254
1,3-(Me3Sn),-bicyclo[2.2.Ilheptane +2.5 CDCI, k 256
I-Me3Sn-CMe-bicyclo[2.2.2]octane + 3.4 CDCI, I 256
1-Me, Sn-adamantane -6.9 25% CH,C1, 254
2-Me3Sn-adamantane - 13.7 25% CH,CI, 254
Me,Sn-CH,CH=CH, + 5.4 CH,CI 4
(ck)-I-Me3Sn-5-Me-2-cyclohexenyl -0.29 C6D6 rn 102,257
 (trans)-1-Me, Sn-5-Me-2-cyclohexenyl -2.72 C6D6 rn 102,257
1-Me,Sn-3,4-Me2-6-Ph-3-cyclohexenyl - 5.2 C6D6 n 101
7-Me, Sn-norbomene (syn) -11.3 25% CH,Cl, 254
- 13.2 C6H6 258
7-Me3Sn-norbomene (anfi) -25.6 25% CH,C1, 254
5-Me3Sn-2-norbomene (exo) +7.8 C6H6 258
5-Me, Sn-2-norbomene (endo) - 1.2 C6H6 258
3-Me, Sn-nortricyclene -11.4 C6H6 258
Me,Sn-CH,Ph +4 50% H,CI, 9
+ 3.57 0.25 M CDCCI, U 164
l,2-(Me,SnCH,),C6H, + 3.76 C6D6/CD2C12 259
l,3-(Me3SnCH,),C6H, +2.20 C6D6/CD2C12 259
1,4-(Me,SnCH2),C6H, +0.98 C6D6/CD2C12 259
Me,Sn-CH,(C,H,-o-OMe) +2.94 C6D6/CD2C12 259
Me, Sn-CH,(C6H,-o-NMe,) -0.78 C6D6/CD2C12 259
Me, Sn-CH,(C,H,-o-PPh,) +3.35 C6D6/CD2C12 259
00
21 Me,Sn-CH,-CHEtC=CH -4.7 cDc1, 245
Me,SnCH,- 1-naphthyl + 9.97 CDC1, 164
Me3SnCH,-2-naphthyl +4.88 cDc1, P 164
l-Me,Sn-CMe- 1,Cethano- 1,2,3,4-tetrahydronaphthalene -3.89 CDC1, 4 164
Me, Sn-CH,CI +4 C6H6 C 8
Me&-CH, Br +6 C6H6 8
Me,Sn-CHCl, + 33 C6H6 8
Me,Sn-CHBr, + 42 C6H6 8
Me&-CCl, +85 90% C6H6 8
Me&-CBr, + 101 90% C6H6 8
Me&-CH,SiMe, +7.6 CDC1, 170
Me,Sn-CH,GeMz, + 11.6 CDCl, 170
Sn)Z CH2 +23.3 C6D6 243
(Me,SnCH,),SnMe, +22.2 (Me@) CDCI, 170
+45.5 (Me,Sn)
 TABLE 3 (cont.)
Compound 6"'Sn Solvent Footnotes Reference
(Me,SnCH,),SnMe +22.5 (Me,Sn) cDC1, 170
+67.7 (MeSn)
(Me,SnCH,),Sn +20.9 (Me&) CDCI, 170
+87.4 (Sn)
Me,Sn-CH,SnMe,-NEt, +20.6 (Me&) Toluene-d, 100
+75.0 (Me&)
(Me,Sn),CHMe +27.5 C6D6 243
(Me, Sn),CHEt + 19.5 CDCI, 243
(Me,Sn),CHPh + 17.8 CDCI, 243
(Me,Sn),CH(C,H,-p-Me) + 17.4 CDCl, 243
(Me,Sn),CH(C,H,-p-OMe) + 17.0 CDCl, 243
(Me,Sn),CMe, + 30.9 CDCI, 170
7,7-(Me,Sn),-norcarane +36.8, -2.0 C6D6 243
(Me,Sn),CH +41.0 C6D6 243,212
(Me,Sn),CEt + 34.1 CDCL 170
(Me,Sn),CC,H,, +35.0 CDCI; 170
(Me, Sn), CCH,Ph +34.7 CDCI, 170
(Me, Sn),CCH,OPh +30.9 CDCl, 170
(Me,Sn),C(CH,),OPh +37.8 CDCl, 170
(Me,Sn),C +49.8 C6D6 243,212
Me&-CH,Ti(C,H,),Cl + 14 C6H6 260
Me&-CH,Ti(C,H,),CH,SiMe, +4 C6H6 260
Me&-CH,Zr(C,H,),Cl + 15 C6H6 260
Me, Sn-CH, Hf(C, H,),Cl + 16.5 C6H6 260
[(Me&Wz {CO,(CO)~11 + 15.0 CDCI, 252
[Me,Sn(Ph)C, {CO,(CO)~}I +20.7 CDCI, 252
Me, Sn-C, H, +26.0 CCI, C 26 1
+32.3 THF-d, 76
(Me3Sn)2C5H4 + 10.6 CCI, C 26 1
1-Me, Sn-indene +31.3 - 261,262
Me Me

Me&E t a : : M e 3 + 34.0 CDCl, r 263

I
Et
Me&-Ph -28.6 20% CH,CI, c,s 254
1-Me&-naphthalene -31.8 25% CH2CI2 254
2-Me3Sn-pyridine -56.7 95% C6D6 264
3-Me3Sn-pyridine -27.4 95% C6D6 264
CMe,Sn-pyridine -27.8 95% CeD6 264
3-Me3Sn-furane -40.4 CDCI, 265
2-Me3Sn-thiophene -27.5 CDCI, 240,266
3-Me3Sn-thiophene -38.3 CDCI, 240
Me,SnCH=CH, -39 10% CCI, C 2
Me,SnC(Me)=CH, -34 CDCI, 90
Me,SnCH=CHMe (cis) - 58 CDC1, 90
Me,SnCH=CHMe (rrans) -42 CDCI, 90
Me,SnCH=CHPh (cis) -50.8 C6D6 102
Me,SnCH=CHPh (trans) -32.2 C6D6 102
Me3SnC(COzMe)=CH2 -27.8 C6D6 102,257
Me, SnCH=CHCO, Me (cis) -51.2 C6D6 102,257
Me,SnCH=CHCO,Me (trans) -32.5 C6D6 102,257
&Me, Sn-bicycle[3.2.1]-octa-2,&diene -47.1 ? 267
7-Me3Sn-bicyclo(3.2.1]-octa-2,ddiene -46.3 ? 267
 TABLE 3 (cont.)
Compound 6'I9Sn Solvent Footnotes Reference

I\
/c=c /Ph + 12.5 ? 268
Me,Sn \H
I\ /CH,Ph
,c=c +4.4 ? 268
Me,Sn \H

1\c=c /H
Me& ' \Ph
-1.7 ? 268

I\ /H
,c=c - 10.7 ? 268
Me,Sn 'CH,Ph
(b)
H /SnMe,
:"=C,,
Me,Sn
(a)

H -52.3 (a)(b) CDCI, 25 1

Me -69.7 (a) CDCI, 241
-45.5 (a)
Bun -70.7 (a) CDCI, 24 1
-47.6 (b)
Bu' -69.2 (a) CDC1, 24 I
-47.0 (b)
 Ph -68.4 (a) CDCl3 24 1
-43.3 (b)
CH,Ph - 68.4 (a) CDCI, 24 1
-43.3 (b)
CH,OMe -68.8 (a) CDCI, 24 I
-46.1 (b)
CH,OPh -65.4 (a) CDCI, 24 1
-43.4 (b)
Me,SnCH=CHSnMe, (cis) -60.5 CDCI, 25 1

(a)

Me3%,/c=c /H
Me3% R'
(b)

R
w
L -
H - 19.3 (a)(b) CDCI, 170,241
CH, - 15.7 (a) CDCI, 170,241
-45.0 (b)
Bun - I58 (a) CDCI, 170,241
-45.6 (b)
Bu' - 1 . 1 (a) CDCI, 170,24I
-46.8 (b)
Ph -9.6 (a) CDCL, 170,24 1
- 38.0 (b)
CH,OMe -9.9 (a) CDCI, 170.24 1
-43.9 (b)
CH,OPh -9.4 (a) CDCI, 170,241
-40.5 (b). .
OPh - 7.2 (a) CDCI, 170,241
-28.3 (b)
 TABLE 3 (cont.)
Compound 61'9Sn Solvent Footnotes Reference

R2>c=c /R3
Me& 'BR',
R' R2 R3

Et H Et -55.3 CDC1, 245

Et Et H -41.2 CDCl, 16
Et Me Et -48.0 CDCI, t 16
Et Ph Et -51.3 CDCI, 246
Pr' H Pr' - 52.1 CDCI, 16
Pr ' Me Pr' - 54.6 CDCl, 16
Pr' Ph Pr ' - 55.2 CDCI, 16
Pr' CeCSnMe, Pr ' 42.0 CDCI, 269
-68.6 (SnC=)
C8H14 Et -60.5 CDCl, u,v 210
C8H,4 Me Et -41.6 CDCI, u,w 210
C8H14 Bu' H -35.5 CDCI, U 211,212

R2, ,BR',
,c=c
Me& 'R3
R' R2 R3

Et H Et -55.3 CDCl, 245

Et Et H -31.2 cDC1, 16
Et Me Et -55.6 CDCI, 16
Et Et Me -58.4 CDCl, 16
C8HU H Et -63.2 CDCl, u,v 210
Et Me& Et -48.0 (R') CDCI, t 16
- 54.6
Me,SnC(Me)=C=CHMe -13.8 25% CH,Cl, 254
(Me,Sn),C=C=CHSnMe, -4.0 (Sn,C=) C6D6 248
-9.3 (SnCH=)
(Me,Sn),C=C=C(SnMe,), +3.1 C6D6 248
(Me,Sn),C=C=CH-C=C-SnMe, + 1.7 (Sn,C=) CDCl, 273
-69.8 (SnC)
Me,SnC(Bu')=C=C(Et)CH,SnMe, -24.0 (SnC=) CDCI, 245
-0.3 (SnCH,)
Me,SnC(SiMe,)=C=C(Et)CH,SnMe, -14.1(SnC=) CDCl, 245
-2.8 (SnCH,)
(Me,Sn), C=C=C(Et)CH,SnMe, - 12.2 (Sn,C=) CDCl, 245
- 1.1 (SnCH,)
Me,SnC(Bu')=C=C(Et)CH(BEt,)SnMe, -20.6 (SnC=) CDCI, 245
+0.2 (SnCH)
Me,SnC(Bu')=C=C(Et)C(Me)(BEt,)SnMe, -24.1 (SnC=) CDCI, 245
-2.8 (SnC)
(Me,Sn),C=C=C(Et)CH(BEt,)SnMe, - 10.9, - 14.7 (Sn,C=) CDCI, 245
-4.9 (SnCH)
(Me,Sn),C=C=C(Et)C(BEt,)(SnMe,), -9.9 (Sn,C=) CDCI, 245,274
-3.2 (Sn,C)
(Me,Sn)C(SiMe,)=C=CHC(SiMe,)(BC,H,,)SnMe, - 12.6, - 12.8 (SnC=) CDCl, U 23.271
+ 1.7, +2.6 (SnC)
(Me,Sn),C=C=CHC(BC,H,,)(SnMe,), -9.6 (Sn,C=) CDCI, Y 23,271
+9.0 (Sn,C)
Et

Me,SnC(Bu')=C=C
(a) %by

R=Me -27.1 (a) CDCI, 245

+69.8 (b)
R = Et -27.0 (a) CDCI, 245
+ 77.8 (b)
 TABLE 3 (con?.)
Compound 6119Sn Solvent Footnotes Reference

Me,Sn-C=C-H -68.1 CH,CI, 91

-70.1 THF/C6D6 76
Me,&-C-C-Me - 73.8 C6D6 157. 159
-73.2 CDCI,
Me, Sn-CEC-Bu" - 73.0 ? 156
Me,Sn-C-C-Bu' -72.7 C6D6 159
-72.5 CDCI, 159
Me,Sn-C-C-C,H, I -73.1 ? 156
Me,%-C=C-Ph -66.3 ? 156
-69.0 CDCI, 157
Me,Sn-C=C-C(Me)=CH, -67.0 C6D6 159
-66.7 CDCI, 159
p Me,Sn-CCC-CH=C(Me)NEt, -72.5 CDCI, 273
Me,&-CEC-C(SnMe,)=C(Pr')BPr', -68.6 (SnCE) CDCI, 269
-42.0 (SnC-)
Me, Sn-C=C-CH=C=C(SnMe,), -69.8 (SnCE) CDCI, 273
+ 1.7 (Sn,C=)
- 59.9 C6D6 158
-61.5 C6D6 158
-59.0 CDCI,
Me, Sn-C=C-OEt -61.5 C6D6 157
Me,Sn-C=C-SiMe, - 75.9 C6D6/CDCI, 157
Me,Sn-C=C-GeMe, - 75.2 CDCI, 157
Me,%-C=C-SnMe, -80.9 C6D6 159
78.0 CDCI, 159
Me,%-C-C-PbMe, -84.0 C6D6 159
-81.0 CDCI, 159
truns-[Pt(C=C-SnMe,),(PEt,),l -93.7 C6D6 253
Me,SnC(SiMe,)N, +35.8 275
 +37.8 275
+ 755 Toluene X 276

For more S1l9Sn data of organotrimethyltin compounds see review 3 and references 371-377.
Reference compound, 61'9Sn is little affected by different solvents and concentration; see, e.g., reference 10.
For other conditions see review 3.
Deuterated in 1-position.
' Deuteration in positions 4, 3,2, and 1 gives the ~5''~Snvalues -0.56, -0.54, -0.50, -0.74, respectively.'02
Deuteration in positions 1 and 4 gives the S1I9Snvalues + 5.31, + 5.30, respectively."'
Deuterated in 2-position.
'The Me,Sn and the Ph groups are in axial and equatorial positions, respectively.
6119Snfor the 2-Ph (endo)-derivative: +4.9 (C,D,).'O'
161'9Sn for the 2-Ph (endo)-derivative: - 16.5 (C,D,).'O1
'b'"Sn values for other 3-substituted (X) I-Me3Sn-bicyclo[2.2.1]heptanesin CDCI,. X = OMe (-3.1). F (- 1.83).256
' S119Snvalues for other 4-substituted (X) I-Me3Sn-bicyclo[2.2.2]octanes in CDCl,, C-C,H,,. X = CN (10.0,9.19), F (1 1.67, 10.83), CI (10.35,
9.66),Br(11.67, 10.95),1(14.08, 13.37),NMe2(6.17, 5.11),0Me(8.76,7.65),Ph(4.9,4.46),C,H4-p-F(5.32, 5.05). Bu'(2.04, 1.89),Me3Sn(-5.53,
- 5.90).
Deuterated in 3-position.
" Ph in equatorial and Me,Sn group in axial position, deuterated in 6-position; S'I9Sn for Ph and Me,Sn both in equatorial positions in C,D,:
-3.4.'01
S1I9Sn values for other substituted (X) benzyltrimethylstannanesin CDC1,. X = p-OMe (1.51), p-Me (1.77), p-F (3.47), rn-OMe (3.99), p-Ph
(4.04), pC1(4.81), m-F (6.00), m-CI (6.49), m-CF, (7.44), o-OMe (3.80).'64
for Me,SnCH,-1-(6-Me)naphthyl in CDCI,: 4.3.164
6'I9Sn for 6- or 7-substituted (X) I-Me3Sn-4-Me-1,4-ethano-l,2,3,4-tetrahydronaphthalenes in CDCI,: X = 6-F (-2.84), 7-F (-2.74), 6-NMe2
(-4.09), 7-NMe' (-5.22), 6-N02 (- 1.64), 7-N02 (-0.77).16'
' The Me,Sn groups migrate about the BC4 ring.
' See review 3 for an extensive collection of substituted phenyltrimethylstannanes.
' The value obtained by 1H{"9Sn} NMR246is less accurate, see also Fig. 9.
" BC,H 14 = 9-borabicyclo[3.3.llnonane.
" ~ 3 ' ' ~ Sof
n the isomer 9-ethyl-10[2-trimethylstannyl-(E)-ethylidene]-9-borabicycl0[3.3.2'~~]decane, -60.4; of the (Z) isomer, -65.6.
S 'I9Sn of the isomer 9-ethyl-10[2-trimethylstannyI-(Z)-propylidene)-9-borabicycl0[3.3.2'~~]decane, -45.9.
To low-field relative to diamagnetic [(Me,SnC,H,),Fe] (61'9Sn, -4.2); ~5"~Sn value is temperature dependent: 307.9 K, + 755; 318.5 K, + 731;
329 K, + 709; 344.9 K, + 689; 360.7 K, + 670.
 96 BERND WRACKMEYER

TABLE 4
Orgaootriethyltin compounds, tin coordination number 4"
Compound 6119Sn Solvent Notes Reference

,
Et SnMe +9.0 20% CCI, 211
Et,Sn + 1.4 20% CCI, b,c 262,211
Et,SnBu' -0.5 - 163
(Et,SnCH,CH,), -1.1 95% C6D6 99
Et,Sn-CH,Ph -6 saturated CCI, 211
[Et,SnCz HC%(CO)6I + 10.6 CDCI, 211
[(Et&)zCzCoz(CO)61 + 2.3 CDCl, 252
Et,Sn-Ph -34 25% eel, 211
Et, SnCH=CH, -42 50% eel, 211
Et,SnCH=CHSnEt, (trans) - 59.4 CDCl, 251

R2'c=c
'
/R3

Et,Sn 'BR,~
R' R2 R3
Et H Et -51.3 CDCI, 212
Et Me Et -41.3 CDCI, 212
Et SnEt, Et -42.0 CDCl, 212
-42.2 (R')
(Et,Sn),C=C=C(Et)C(BEt,)(SnEt,), - 19.4 (SnC=) CDCI, 212
-1.8 (Sn,C)
(Et,Sn),C=C=CHC(BC,H14)(SnEt,), - 19.9 (Sn,C=) CDCl, d 212
-4.8 (Sn,C)
Et Sn-C=CH -52 30% CCI, 211
- 56.5 C6D6 159
- 56.3 CDCI, 159
Et,Sn-C=C-Me - 56.1 C6D6 159
- 56.4 CDCl, 159
Et,Sn-C=C-SnEt, -60.2 C6D6 159
-60.0 CDCI, 159

For more 6119Snvalues of organotriethylstannanes see review 3.

* For other conditions see review 3.
This appears to be the correct value, in agreement with recent direct PET '"Sn-NMR measurement^.'^
' BC8H14= 9-Borabicyclo[3.3.1]nonane.

shift of the l 19Snresonances ta lower frequenciesin going from tetrahedral to

trigonal-pyramidal or octahedral symmetry is particularly convenient for
studying even weak donor-acceptor interactions in solution. This includes
covalent solute/solvent interaction, autoassociation, and/or intramolecular
coordination.
There are, of course, other factors to be considered besides the coordination
number. These are mainly related to the presence of low-lying excited states
 Sn-NMR PARAMETERS 97

TABLE 5
Org~aotri.Uryl(C,H,, C,H,, C,H,,) tin compounds, coordinationoumber = 4"

Compound aLL9Sn Solvent Notes Reference

Pr",Sn - 16.8 - 278

Pr",SnBu' -11.8 - 99
Pr",SnCH=CHOBu" - 50.6 CCI, 279
Pr',Sn -43.9 - 218
-42.6 ? 280
Pr',SnBu' -42.6 C6D6 86
h',SnBu' -48.7 - 99
Pr',Sn-chex - 55.4 ? 280
Bu",Sn - 12.0 - 28 1
-6.6 CCI, 262,279
-11.5 cDc1, 161
Bu",SnBuS - 14.1 C6D6 86
Bu",SnBu' -7.9 - 99
1-Bu",Sn-norbornane (em) - 13.5 C6D6 b,c 101
1-Bun,Sn-norbornane (endo) -12.4 C6D6 b,d 101
1-Bun3Sn-2-Ph-chex -21.8 C6D6 b,e 101
(cis)-1-Bu",Sn-5-Me-2-cyclohexenyl - 18.7 C6D6 102,282
(trans)-1-Bu",Sn-5-Me-2-cyclohexenyl - 19.6 C6D6 102,282
Bun,SnCH,OEt - 37.4 C6D6 364
1-Bu",Sn-3,4-Me2-6-CO2Me-3-cyclohexenyl- 13.0 C6D6 fg 101
Bu",SnCH(CI)OEt -28.2 C6D6 364
Bu",SnCH(OEt), - 57.8 283
Bu",Sn-Ph -41.7 - h 284
Bu",SnCH=CHPh (cis) - 56.0 C6D6 102
Bu",SnCH=CHPh (trans) -43.2 C6D6 102
Bu",SnCH=CHBu" (cis) -60.8 C6D6 102
Bun,SnCH=CHBu" (trans) - 50.3 C6D6 102
Bu",SnC(Pr")=CHPr" (cis) -53.5 C6D6 102
Bu",SnC(CO, Me)=CH(CO,Me) (cis) -37.8 C6D6 102
Bun3SnC(CO2Me)=CH(CO,Me) (rrms) -20.5 C6D6 102
Bu",SnCH=CH(CO,Me) (cis) - 57.6 C6D6 102
Bun3SnCH=CH (CO, Me) (tram) -46.0 C6D6 102
Bu",SnC(CO,Me)=CH, -40.0 C6D6 102
Bu",SnC(Me)=CH(CO,Et) (cis) -52.7 C6D6 102
Bu",SnC(CO,Et)=CHMe (cis) -48.6 C6D6 102
Bu",SnC(CO,Et)=CHMe (trans) -32.9 C6D6 102
Bu",SnCH=C(Et)BEt, (cis) -62.2 CDCI, 272
(Bu",Sn),C=C(Et)BEt, - 53.7 (cis) CDCI, i 272
-55.2 (trans)
(Bu",Sn),C=C=C(Et)C(BEt,)(SnBu",), -28.3 (Sn,C=) CDCl, 272
- 18.9 (Sn,C)
(Bu,Sn),C=C=CHC(BC,H,,)(SnBu",), -27.5 (Sn,C=) CDCI, j 272
- 14.0 (Sn,C)
Bu",Sn-C=C-H -69.0 CDCl, 161
Bu",Sn-C=C-SnBu", -74.3 CDCI,
Bu',SnBu' -27.4 c6 D6 86
 98 BERND WRACKMEYER

TABLE 5 (cont.)
~

Compound 61'9Sn Solvent Notes Reference

Bu',Sn -45.2 C6D6 86

-45.34
-45.16

Bu',SnMe -25.4 - 4
(Bu'CH,),SnBus -40.6 C6D6 86
____~ ~

For more 6'I9Sn data of organotrialkyltin compounds see review 3.

Deuterated in the 2 position.
' 6119Snof the 2-Ph(exo) derivative: - 1l.l.'o'
'
~5''~Sn of the 2-Ph(exo) derivative: -26.4.'"
The Bu",Sn and Ph groups are in axial and equatorial positions, respectively.
'
Deuterated in 6 position.
The Bu",Sn- and C0,Me- groups are in axial and equatorial positions, respectively; 6'I9Sn
of the isomer with both groups in equatorial positions: - 15.5.
For other conditions see review 3.
See Fig. I .
j BC, H , 9-Borabicyclo [3.3.I] nonane.

and to the effective nuclear charge of the tin atom. Frequently, these
influences mask each other and their separation is difficult. A proper example
for a consideration of the effects of paramagnetic circulation of charge is
found in the monomeric bis[N,N-bis(trimethylsilyl)amino]tin(II), which has a
bent structure (N-Sn-N angle = 96") in the vapour phase.74 It can be
assumed that circulation of charge from the trigonal plane into the
underoccupied tin p z orbital deshields the tin atom as evidenced by the
'
extreme high-frequency shift of the 19Snr e ~ o n a n c e . ' ~This
. ~ ~corresponds
~

TABLE 6
Various tetraakyltin compounds, tin coordination number = 4

Solvent Reference

+I 20% CCI, 211

-2 80% C,H6 8
-4.5 - 89
- 3.0 CDCI, 16
+ 11.5 - 4
+53.5 89
-42.5 89
+ 121 4
- 80 4
 "Sn-NMR PARAMETERS 99
TABLE 7
Organotriphenyltincompounds, tin coordination number = 4"
Compound 6119Sn Solvent Footnotes Reference

Ph,SnMe -98 30% CCI, 277

-93 CH,CI, 8
Ph,SnEt -98.6 C6D6 285
Ph, SnPr' - 106.7 C6D6 285
Ph,Sn-cPr - 105.2 C6D6 285
Ph,Sn-Bun - 101.5 C6D6 285
Ph, Sn-Bus - 105.5 CDCI, 86
Ph,Sn-cBu - 101.5 C6D6 285
Ph,Sn-chex - 113.7 CHCI, 278
Ph,Sn-CH,chex - 103.1 C6D6 285
a b
Ph,Sn(CH,),CH(Me)SnPh, -95.5 C6D6 286
- 90.2
Ph,Sn-CH,CH(Me)Ph - 107.3 C6D6 285
Ph,Sn-CH,CH=CH, - 123.2 C6D6 285
Ph,Sn-CH,CH,CH=CH, - 100.9 C6D6 285
Ph,Sn-CH,Ph - 118.0 C6D6 285
Ph,Sn-CH,- I-naphthyl - 118.6 C6D6 285
Ph, Sn-CH, SPh -118 CH,CI, b 133
Ph,Sn - 128.1 CDCI, c 66
Ph,SnCH=CHPh - 132.4 C6D6 285
Ph,Sn-CEC-H -171.0 CDCI, 16
Ph,Sn-C-C-SnPh, -176.1 CDCI, 76
Ph,Sn-C(S)SMe - 192 CH,CI, 281
Ph,Sn-C(S)SCH,Ph - 191 CH,CI, 287
Ph,Sn-C(S)SC,H, - 192 CH,CI, 287
Ph, Sn-C(S)NHMe -49 CH,CI, 287
Ph,Sn-C(S)N(CH,), - 55 CH,CI, d 287
Ph,Sn, ,S, ,PPh,
,c-Pt
R 'PPh,
R

SMe - 185 CH,CI, e 287

SCH,Ph - 182 CH,CI, e 287
SC,H, - 184 CH,CI, e 287
NHMe - 54 CH,Cl, e 287
N(CH2)4 - 56 CH,'CI, d,e 287

For other organotriphenyltin compounds see review 3 and references 370 and 371.
'The sign in review 3 for this 6119Snvalue and for the 6Il9Sn values of the analogous
compounds Ph,SnCH,-S(C6H,-X) should be negative, as given in review 288.
For other conditions see review 3; this value is believed to be correct.
In the paper the amino group is given aspyrr, with N-pyrrolyl in the text but N(CH,), in the
scheme.
' 2J(195Pt119Sn): 237-250 Hz.
100 BERND WRACKWYER

to a high-frequency shift of
amides (see Table 19).
- 700 ppm with respect to the trimethylstannyl-

Me,Sf
I
N
Me,Si' \S n S
6'19Sn + 775 in C,D,, 80°C
Me Si
N'
I
Me,Si

In contrast to the monomeric stannylenes the "9Sn resonances of

bis(cyclopentadieny1) derivatives of Sn(I1) are found at exceptionally low
~ . ~ ~ 8). Molecular orbital calculation^^^ assign the highest
f r e q ~ e n c y(Table
occupied molecular orbital (HOMO), 3a, ,of the bent (C,H,),Sn molecule79
to the nonbonding electron pair on the tin atom. However, the antibonding
MO, 2b,, in the stannocene, corresponding to the lowest unoccupied
molecular orbital (LUMO)with almost pure p character in the stannylenes, is
expected to lie at rather high energy. This prevents efficient paramagnetic
charge circulation as shown by the highly shielded tin atoms in stannocenes.
Similar arguments, based on MO calculations for [(C,H,)Sn]+,78 predict a
highly shielded tin atom in the pentamethylcyclopentadienyltin cation in spite
of the positive charge. Accepting the a complex ( q 5 ) structure of the
(C,H,)Sn(II) compounds we find again that a high coordination number of
the tin atom is related to high shielding [see, for comparison, 6119Sn of
q'-cyclopentadienyltin(1V) compounds, Table 81.
On the other hand, both the effective charge of the tin atom and high
coordination number may be invoked to account for the highly shielded tin
atoms in the naked nonrigid polyhedral anions like [Sn9I4- (6119Sn-123080*81)
or [Sn,]'- (6"'Sn - 1895)" (see Table 21). MO calculation^^^ of these
clusters corroborate this with respect to the charge of the tin atoms (e.g., in the
series [Sn8GeI4-, [Sn9I4-, [sn8Pbl4-).
 '"Sn-NMR PARAMETERS 101

TABLE 8
Tetraorganyltin wmpouods, tin coordhtiaa number 3 4"

Compound 6'19Sn Solvent Footnotes Reference

(CH,=CH-CH,),SnBu" -34.3 - 279
(CH,=CH-CH,),Sn -47.9 - b 219
(PhCH,),SnEt, - 13 40% CH,CI, 277
(PhCH,),SnEt -23 40% CH,CI, 277
(PhCH2)4Sn -36 CH,CI, 289
(C5H5)2SnMe2 + 23 CCI, 261
(C5H5),SnMe - 7.0 CCI, 261
(C,H,),Sn -24.4 CCI, d 261
-27.2 ? 77
(CSH5)2Sn -2199 C6H12 4
(C5H4Me)2Sn -2171.1 CDCI, 77
Ph,SnMe, -60 - 278
(pCH,=CH-C6H,),SnMe, - 56.2 286
Ph,SnEt , -66
C6D6
50% CH,CI, 277
Ph,SnBu", -65.9 - 278
(pCHz=CH-C6H,),SnBu", -69.4 CDCI, 286
Ph2Sn(CH2)4 0 CHZCI, (96,290)
Ph2Sn(CH2)5 -66 CH,CI, (96,290)
- 107.7 C6D6 286
(pCH,=CH-C6H,),Sn(CH,), - 106.2 C6D6 286
Ph2Sn(CH2)6 - 57.4 40% CH,CI, 4
Ph,Sn(CH,),SnPh, - 74 CHZCI, (96,290)
Ph,Sn(C,H,-p-CH=CH,), - 126.2 C6D6 286
(pMe-C6H,),Sn(C,H,-pCH=CH2), - 122.3 C6D6 286
(pCH2=CH-C6H,),Sn - 123.9 C6D6 286
(3-furyl),SnMe2 -80.1 CDC1, 265
(3-furyl),SnMe - 118.9 CDCI, 265
(3-furyl),Sn - 157.4 CDCI, 265
(2-thienyl),SnMe2 -69.3 CDCI, 266
(2-thienyl),SnMe - 104.5 CDCI, 266
(2-thienyl),Sn - 143.6 CDCI, 240
- 148.6 CDCI, 266
(CH,=CH),SnMe, -79.4 - 278
-84.0 - 3
[CH,=C(Me)],SnMe, -69 CDCI, 90
[CH(Me)=CH],SnMe, (cis.cis) -116 CDCI, 90
[CHMe=CH],SnMe, (truns,tram) - 84 CDCI, 90
[CHMe=CH],SnMe (cis,rrans) - 100 CDCI, 90
[CH,=C(Me)][CHMe=CH]SnMe, (cis) -92 CDCI, 90
[CH,=C(Me)][CHMe=CH]SnMe, (tram) -76 CDCI, 90
(CH,=CH),SnEt, -81 20% CCI, 277
(CH,=CH),SnBu", -86.4 - 278
(CH,=CH),SnMe - 124 - 3
(CH,=CMe),SnMe - 106 CDCI, C 90
 102 BERND WRACKMEYER

TABLE 8 (cont.)
Compound 6'19Sn Solvent Footnotes Reference
[CH(Me)=CH],SnMe (cis) - 175 CDCI, C 90
[CH(Me)=CH],SnMe (trans) - 123 CDCI, C 90
(CH,=CH),Sn - 157.4 CCI, d 279
(CH,=CMe),Sn - 143 CDCI, e 90
[CH(Me)=CH],Sn (cis) - 234 CDCI, e 90
[CH(Me)=CH],Sn (trans) - I62 CDCI, e 90
(HC=C),SnMe, - 153.8 CH,CI, f 91
- 154.5 C6D6 159
(MeC=C),SnMe, - 156.0 CH,CI, 91
- 157.6 C6D6 159
(Bu"C=C),SnMe, - 156.7 ? 156
(Bu'C=C),SnMe, - 157.6 CH,CI, 91
(PhC=C),SnMe, - 147.6 CDCI,
(HC=C),SnEt, -141.0 CCI, 277
- 141.3 C6D6 159
- 141.0 CDCI, 159
(MeC=C),SnEt, - 142.9 C6D6 159
-141.0 CDCI, 159
(HC=C),SnPr', - 141.7 CH,CI, 91
(HC=C),SnPh, - 227.5 CDCI, g 252
(Me,SiC=C),SnMe, - 167.4 CDCl, 157
(MeC=C),SnPh, -225.3 CDCI,
(PhC=C),SnPh, -219.5 CDCI,
(HC=C)Sn(Ph,)C=CSn(Ph,)C=C-H -234.6 CDCI, h 252
(Bu"C=C),SnMe -248.6 ? 156
(HC=C),SnPr' - 244.9 CH,CI, 274
(HC=C),Sn - 356.3 CDCI, i 161
(MeC=C),Sn - 348.0 CDCI, i 159
(Bu"C=C),Sn - 345.9 ? 156

Alkyl, benzyl, cyclopentadienyl, aryl, heteroaryl, vinyl, and alkynyl derivatives. For other tetra-
organyltin compounds see reviews 3 and 4 and references 369 and 370.
Change of the 6'I9Sn value to - 147.5 on dilution with CCI,.
' 6'I9Sn values for the other isomersare assigned as follows:cis, cis, trans (- 158);cis, trans, trans (- 142);
cis, cis, ips0 ( - 150); cis, trans, ips0 ( - 132); trans, trans, ips0 ( - 118); cis, ipso, ips0 ( - 127); trans, ipso, ips0
( - I 12).
For other conditions see review 3.
61'9Sn values for the other isomers are assigned as follows: cis, cis, cis, trans (- 21 I); cis, cis, trans, trans
(- 191); cis, trans, trans, trans (- 175); cis, cis, cis, ips0 (- 208); cis, cis, trans, ips0 (- 187); cis, trans, trans,
ips0 (- 171); trans, trans, trans, ips0 (- 157); cis, cis, @so, ips0 (- 184); cis, trans, ipso, ips0 (- 167); trans,
trans, ipso. ips0 (- 153); cis, ipso, ipso, ips0 (- 162); trans, @so, @so, ips0 (- 149).
61'9Sn of the complex [Me,Sn(C,H),[Co(CO),],]: -4.2 (CDC13).252
6'I9Sn of the complex [ph2Sn(C,H),[Co(CO)6)]z]: - 114.6 (CDC1,).252
6119Snof the complex [(Ph2Sn),(C,)(C,H),Co(CO)6]3]: - 122 (CDC13).2s2
' Obtained by direct 'I9Sn NMR, assignment proved by 'H coupled '19Sn-NMR spectrum; the 6'I9Sn
value -279," obtained by 'H{ '19Sn} INDOR spectra is not correct.
j This corrects a misprint.159
 ’ 9Sn-NMR PARAMETERS 103

2. Substituent eflects and multiple substitution

The shielding of the 19Snnucleus is significantly affected by the number of
various substituents present, and by their electronic and steric properties.
Very often a direct comparison of substituent effects is hampered because
bulky groups, either at the tin atom or at the substituent atom, are required to
prevent autoassociation (e.g., fluorides or alkoxides). The bulk of the valves
of 6’”Sn available concerns compounds containing tin atoms with coor-
dination number 4. The qualitative application of the theory of nuclear
screening predicts major changes in CJ when the tetrahedral geometry is dis-
torted and the symmetry is lowered, e.g., to C3vor C2v.84 This is seen in
Fig. 6, which shows the dependence of the screening of 19Sn in Me4-,SnX,
on the number (n) of groups X. A comparison of the 6’19Sn values for
the compounds SnX, (Fig. 6) reveals that there is no obvious general rela-
tionship between a1I9Sn and other empirical parameters. Instead it appears
that a number of possibly counteracting influences should be considered:
( I ) electronegativity, (2) excitation energies, and (3) neighbour contribu-
tions. It seems that the evaluation of neighbour contributions, in particular,
constitutes a serious problem for the interpretation of tin chemical shifts.
Bearing in mind that at present there is no way of separating the
contributions to tin nuclear shielding, an exceedingly complex situation arises
for the theoretical understanding of lI9Sn chemical shifts. This also emerges
from Fig. 6, in which is seen the familiar “sagging” pattern of the 6119Sn
values depending on X and n; the differing amounts of “sagging” for various
ligands X reflect the aforementioned counteracting influences on tin nuclear
shielding and additional features introduced by the lower symmetry around
the tin atom.85
Therefore, any simplified approach to nuclear screening such as that given
in Eq. (9) is inadequate to interpret 6’19Sn data in more than a qualitative
way. However, from a purely empirical and practical point of view, the picture
in Fig. 6 is encouraging. The ~ 3 l ’ ~ Svalues
n available today are indicative of
the type of substituent X and of the number of substituents present. Hence,
19Sn-NMR spectra may be used to prove the purity of a given tin compound
and to investigate the equilibrium of this compound with other species in solu-
tion and, of course, the dynamic properties in Thus, it is obvious
that already the large range of Il9Sn chemical shifts is in favour of ‘19Sn
NMR being used as a useful analytical tool. The tetra-sec-butyltin molecule
may serve as an instructive example to demonstrate some of these points.
Owing to the presence of four identical chiral centres around the tin atom,
three diastereomeric compounds should exist. Neither ‘H nor I3C NMR
reveals reliable information. However, in the I9Sn-NMR spectra three
signals are found (-45.2, -45.3, -45.8) with relative intensities close to the
predicted ratio, assuming a random distribution (37.5 :50: 12.5).86.87
104 BFRND WRACKMEYER

1 2 a
FIG. 6. Dependence of nuclear screening of Il9Sn on the number (n)of groups X.Compare
Tables 3-9 for tetraorganylstannanes, Table 10 for tin hydrides, Tables 11-13, 20, 24 and 25
(tin-GroupVII), Tables 13-18,21, and 24(tin-GroupVI), Tables 13,14,18-20, and24(tin-
Group V), Table 21 (tin-Group IV),Table 22 (tin-Group III), Table 23 (tin-lithium), and
Tables 24 and 25 (tin-transition metal compounds) for more detailed information.

3. Effects of interbond angles at the tin atom

Many shielding effects, which frequently are hardly noticeable in
NMR, are amplified in "'Sn NMR. Changes in the bond angles brought
upon the system by steric constraints (e.g., ring closure) are reflected by large
 ' Sn-NMR PARAMETERS 105

'
shifts of the 19Sn resonances. This is shown, for example, with tin-sulphur
and tin-carbon bonds. The l19Sn resonance is shifted to significantly higher
frequencies in the five-membered rings; this appears to be a general effect. A
trigonal-bipyramidal five-coordinationof tin in the dimethyldithiostannolane
has been revealed by X-ray studies, with the molecules arranged in a

/SEt
Me,Sn M e , S n\S
/S7) Me,Sn<'] S Me,Sn<S]S
\SEt
+ 127.0" + 149.OS9 + 190.089 + 231.016

Me,SnP M e
&Me

- 1 16.090 - 161.79' + 19S9'

Me,SnPr",

-4.589
Me,Sn
3
-4 2 ~ ' ~
Me,Sn
3
+ 53.589
chain.93*94It has been suggestedg3that the small bond angle ( L S-Sn-S =
89.6') prevails to some extent in solution (in agreement with a 'H-D NMR
study)" and, therefore, accounts for the deshielded tin atom.*' Similar
arguments may be valid in the case of dithiastannolene in which the shielding
of the tin atom is even smaller.
In the cyclic tetraorganylstannanes it is evident that '19Sn NMR is an
extremely sensitive tool for distinguishing between six-membered and five-
membered cyclic compounds95 (see Table 9). In the case of the diphenyl-
stannolane system the presence of a 10-membered ring, the dimer, is readily
shown by l19Sn NMR.96 Again, the shielding of the tin atom in the
stannolane is reduced with respect to the 1,6-distannacyclodecane derivative:

This deshielding appears to be connected with the probability of excitation

of 0 electrons since it is frequently found for other main group nuclei (e.g.,
'lB, "Si, 'O'Pb) in similar bonding situations.
106 BERND WRACKMEYER

TABLE 9
Unsaturated cyclic tetraorganyl tin compounds, tin coordination number = 4

Compound 6'I9Sn Solvent Reference

R' R2 R3

R3 R2 Me Me Me +60.2 CH,CI 291

Me Et Me +55.0 CH,CI, 291
Me Et Ph +75.8 CDCI, 292
Ph Et Me -47.7 CDCI, 76

R' R2 R3 R4

Me Et H H + 19.5 CH,CI, 293

RZ BR2, Me Pr H H + 28.9 CH,CI, 293
\ I
Me Bu" H H + 13.2 CH,CI, 293
Me Et Ph Ph + 14.6 CDCI, 292
Me Pr ' Ph Ph + 16.5 CDCI, 292
Me Me Bu' But + 5.7 CH,CI, 207
Me Et Bu' But + 17.7 CH2CI, 207
Me Et Me Bu' + 15.5 CH2CI, 207
Et Et H H + 36.1 CDCI, 76
Ph Et H H -44.4 CDCI, 76
Ph Et Me Me -71.8 CDCI, 76
P\ Ph

Ph 0 Me,
Ph
+52 CH,CI, 9

R' R2 R3 E

R2 R3 Me H H CMe, - 161.7 CDCI, 91

H Me H H PPh - 158.2 CDCI,

136
136

R"skER2 R3
Me
Me
Me
H
H
H
H
H
H
P(Se)Ph
SiMe,
SnMe,
- 178.9
- 166.3
- 177.5
CDCI,
CDCI,
CDCI,
136
136
136
Me H H BNEt, - 160.0 CDCI, 136
Me Me H BMe - 157.6 CDCI, 136
Me Me H BBu' - 156.0 CDCI, 136
Me Me H BBu", - 149.0 C6D6 136
Me Me H BOMe - 141.0 C6D6 136
Me Me H BNEt, - 143.0 C6D6 136
Me Me Et BEt - 136.5 CH,CI, 29 1
Me Me Pr BPr' - 116.5 CDCI, 29 1
Me Ph Et BEt - 132.0 CDCI, 292
Me Ph Pr' BPr' - 116.5 CDCI, 292
Ph Me Et BEt - 199.3 CDCI, 16
 9Sn-NMR PARAMETERS 107

4. Temperature dependence
As a result of autoassociation or covalent solvent interactions, tin nuclear
shielding depends heavily on temperature. In the absence of these effects the
nuclear shielding will depend on rotation, vibration, electrostatic
solvent-solute interactions, and conformational equilibria within the com-
pound under c ~ n s i d e r a t i o nIt
. ~has
~ been found that the shielding of 1'9Sn
increases roughly linearly with increasing t e m p e r a t ~ r e , ~ * -although
'~~ the
slope of this relationship is expected to depend critically upon the type of
compound and, possibly, also upon the solvent used. A recent studylooshows
the temperature dependence of 6 'I9Sn to indicate different conformational
populations in trimethylstannylhydrazines. According to the projections,
which both show the gauche conformation, the energies of the conformers
depend on the nature of the substituents R' and R2 (and a nonlinear change
of 6119Snwith temperature is observed):

5 . Isotope eflects
It appears'O that all claims of a significant 117/119Snprimary isotope effect
are based on inaccurate measurements. The difference in shielding
6117Sn/6119Sn(expressed in ppm) can be safely neglected."
Secondary isotope effects on the '19Sn resonance, e.g., in deuterated
organotin compounds, have been measured. Direct deuteration ( M ~ , S ~ I D , ) ~
and indirect deuteration [S~I(CD,)],~~ shift the lI9Sn resonance to lower
frequency. However, no recent systematic studies on this subject have been
carried out. In various studies, specifically 'H-labeled tetraorganylstannanes
have been obtained in order to determine the stereochemistry as a function
of nJ(119Sn2H).87*'0'*'02 The 6119Sn values differ very little (GO.1 ppm)
from the values for nondeuterated compounds. Therefore, in routine
'I9Sn-NMR spectra these effects are negligible when considering the
influences of solvent, temperature changes, etc., on the '19Sn resonances
which are of the order of f O . l ppm (even when an attempt is made to
record the spectra under analogous conditions).
The isotope effect 12C/13C[A6'(13C)]in organotin compounds depends on
the nature of the substituents. In addition to the expected effect of heavy

-
isotopic substitution (low-frequency shift) there are examples where
A6i('3C) 0 (see Fig. 7), and frequently, high-frequency shifts of
the "9Sn-resonances are observed.'03 A6'(I3C) in ppm'03: Me,Sn,
-0.018; Et,Sn, -0.020; Me,SnC=CH, k0.002 (Me), -0.059 (CE);
108 BERND WRACKMEYER

(CH,),Sn-C=C- Sn(CH,),

' 'Jc'"Sn''C) [CH,]

*

I I I I I rT'9"Hf-I I I , I I I I I I I I I

FIG. 7. 'I9Sn-NMR spectrum at 74.63 MHz of bis(trimethylstanny1)ethyne in C,D,,

20% w/v, 2 8 T , 'H broadband decoupled;the centre of the '%2H3 satellites corresponds exactly
to the large 'I9Sn resonance (kO.2 Hz)whereas the centre of the satellites is shifted
by 4 Hz = 0.054 ppm to low frequency. This is readily seen from the different intensities
of the I3CH3and "CG satellites and from the fact that both couplings, 'J(1'9Sn'3CH,) and
1J(119Sn'3C~), are of identical magnitude. The 13C satellites from ' J ( l l9SnC=l3C) are
masked by the "'Sn satellites, 13J(119Sn1'7Sn)l= 51 Hz.

Me,Sn(C-CH),, +0.016 (Me), -0.027 (C-); MeSn(C-CH),,

+0.025 (Me), -0.009 (C=); Sn(C-CH),, +0.009.

C. Correlations between *I9Snchemical shifts and other

Group IV element chemical shifts
Since a great number of NMR parameters of Group IV elements are readily
accessible (with the exception of the 73Genucleus), comparing these data for
isostructural compounds is clearly of interest. This has been done frequently,
e.g., for 6'3C/629Si,'04 for 629Si/6119Sn,'05and for 6"9Sn/6207Pb.'05~'06
There are clearly broad parallels between the shielding of 2gSi/"9Sn or
119Sn/207Pb, indicating that (1) the structures in solution are analogous and
(2) the influences of various ligands can be compared with respect to bond
polarity and excitation energies. Thus, the slopes of the straight lines resulting
from the roughly linear correlations d2'Si/6' 19Snand 6' '9Sn/6207Pbshould
correspond to the ratios of the radial expansion terms ( r - 3 ) n p .This is found
to be the case for the correlation 6119Sn/629Si(5.1,'05 to be compared with
4.5).46 The deviation of the slope from the expected ratio of the radial

-
expansion terms becomes much larger in the case of the 6207Pb/6119Sn
correlation (slope 3.0, ratio ( r - 3 ) 6 , / ( r - 3 ) 5 , = 1.4/1.9).
 "Sn-NMR PARAMETERS 109

It is likely that the calculation of values of (r-3),,p becomes less reliable for
heavy atoms. The correlation 6l "Sn/d207Pb reported in the l i t e r a t ~ r e ~ ~ ~ * ' ~ ~
can be extended to include the 611'Sn and Sto7Pb values of the polyhedral
anions [Sng-,,Pb,,14-. However, the 6 values of the monomeric Sn(I1) and
Pb(I1) amides deviate considerably from the linear correlation. From the
6"'Sn value of bis[bis(trimethylsilyl)amino]tin(II) (+779, a d207Pbvalue
of N + 1800 to +2400 would be predicted for the analogous Pb(I1) com-
pound in contrast to the experimental value d207Pb= +4916.76

V. INDIRECT NUCLEAR SPIN-SPIN COUPLINGS, "J("'SnX)

A. General
The valence electron-mediated nuclear spin-spin coupling, J, is a scalar
quantity and may be obtained directly from NMR spectra, in the present case
either from "'Sn- or X-NMR spectra. Since theoretical treatments of
spin-spin couplings have been excellently described41*107-' this summary
concentrates on some aspects which are believed to be of major importance
for "Sn-X spin-spin couplings.
According to Ramsey's formulation of the spin-spin coupling energies, lo7
coupling involving electrons is described by more than one mechanism. The
interaction between the nuclear magnetic moments and the electron orbital
motion (spin-orbital term), and the dipolar interaction between the nuclear
spins and the electron (spin-dipole term), are, in general, considered to be of
minor importance in comparison to the contact term. The latter term takes
into account the possibility that the electron may be found in the same place as
the nucleus, as predicted by quantum mechanics. Although there is little
theoretical and only limited experimental evidence, the contact term is
assumed to dominate the coupling even when the heavier nuclei are involved.
As in the nuclear screening, B, infinite summations over excited electronic
states have to be taken into account in describingJ. Fortunately, in contrast to
B, there is no gauge dependence problem to be considered in calculations of
couplings, and the questionable reliability of results based on the difference of
two more or less inaccurate parameters (upand nd)is no problem. Therefore,
most of the calculations or discussions of couplings do not suffer from too
gross approximations, although we are still far from a detailed comprehension
of all the data available. Various procedures have been developed to calculate
13-' '
However, for a more qualitative discussion, the original
approach of Pople and Santry"' is of advantage.
The contact term can be expressed, in Pople and Santry's MO treatment
(independent electron model), as shown in Eq. (10),'09
KAB = ~ 1 1 0 2 1 1 B 2 1 1 s \ ( o ) 2 ~ B ( 0 ) z ~ ~ B (10)
110 BERND WRACKMEYER

where K is the reduced coupling for nuclei A and B [KAB =

(h'/h)J~~(y,&-'], po is the permeability of free space, pB is Bohr's
magneton, t,bA(0)', t,bB(0)?are the respective valence s electron densities, and
nABis the mutual polarizability of the A and B s orbitals.
The mutual polarizability term (nAB) represents the difference of one-
electron energies. Clearly, both the magnitude and sign of KAB reside in this
term. By assuming constant values of singlet excitation energies, an average
excitation energy, AE, is introduced'08 and ZAB is replaced,

leading to values K A B which are always positive and are linearly related to the
"s character" (Pg(A)s(Bb)of the A-B bond. This approach is extremely
simplified and its application to nuclear spin-spin coupling involving heavy
atoms, multiple bonding, or nuclei carrying lone electron pairs is not justified.
Indeed, it seems that the interpretation of most of the features observed for
'J(SnX) requires one to consider the mutual polarizability term nsnx. In
addition, it has been pointed out that in the case of heavy nuclei, such as Sn or
Pb, the relativistic analogue of Ramsey's theory should be used. Examples are
given by calculations of spin-spin coupling tensors using a sum-over-states of
relativistically parameterized extended Huckel (REX) wave functions.' 16,117
From this it appears that cautious use of nonrelativistic atomic valence s
electron densities, t,bsn(0)', is advisable."7
The dominance of the contact energy for tin spin-spin couplings implies
that the parameter J(SnX) is useful in discussionsof structure and bonding. In
this regard one is tempted to follow the well-known arguments available for a
great number of carbon couplings. Accordingly, one finds many parallels
between values of J(SnX) and J(CX). 12,13 However, at the same time, there
are many data pairs deviating from this concept. This indicates the additional
influence of the large and polarizable "'Sn nucleus leading to differing
contributions to the contact interaction via the mutual polarizability term.

B. Patterns of couplings, "J(SnX)

1. One-bond couplings, 'J( 1'9SnX)
There are a great number of 'J("'SnX) values available for X taken
'
throughout the periodic table. Reduced couplings, ' K ( "SnX), are given in
Table 26 together with corresponding values of 'K(13CX), 'K("SiX), and
1K(207PbX).There are fairly regular changes of 'K(EX) (E = I3C, 29Si,
"'Sn) in the case of X = 'H, "B, I3C, "Si, "'Sn, '07Pb, IE3W, and the
increase of 'K(EX) with increasing size of E corresponds to the change of
valence s electron densities t,bE(0)'. This is no longer true for many values of
1K(207PbX)'3."8 as a result of the large polarizability of this nucleus
 "'Sn-NMR PARAMETERS 111

together with the possible influence of relativistic effects concerning the Pb 6s

electron^,"^ which cannot be simply included in the value of t,bE(0)2.The
relationship between the 'K(EX) values also breaks down for X = "N,
31P(III), 31P(V), 77Se, 125Te.'2 There are not enough data available for
couplings to fluorine. All these X nuclei have either lone electron pairs or the
Sn-X bond is much more polar [e.g., Sn-P(V)] than the corresponding
C-N bond. This gives an indication that, in general, we would expect to find
more negative contributions to the contact term in the case of Sn-X nuclear
spin-spin couplings as compared with C-X or Si-X interactions. This means
that, in all comparable compounds for which 'K(13CX) or 'K(29SiX)may be
of either sign, a negative sign for 'K(1'9SnX) is likely.
The comparison between ' K ( "Hg "'Sn), ' '
K(' 5Pt 'Sn), and
1K('99Hg'3C), 1K('95Pt'3C) shows that the former values for 'Jseem to be
very large, but again the ratio of the 'Kvalues differs very little from the ratio
of the valence s electron densities t,b,,,s,(0)2/t,b,,c(O()-8).363
2
a. 'J('"Sn'H). Values of 'J("'Sn'H) are listed together with the
~5''~Sn data for some tin hydrides (Table 10). Of course, there are many more
data in the literature for compounds which have not been studied by "'Sn
NMR.
In alkyltin hydrides the magnitude of 11J(1'9Sn'H)I increases with n in the
series R4-, SnH, (n = 1,2,3,4) and decreases with an increase of branching
in the alkyl group:

J(IL9Sn'H)(Hz)

R R,SnH R2SnH, RSnH, SnH,

Me - 1744''9 - l797Iz0 - 1852'19 - 1930'20

Et - 1613'21 - 1690'21 '
- 1790' -
Pr - 1505122 - 1608'20 - 175OLZ2 -
Bu' - - 1554'22 - -

In the series of phenyltin hydrides Ph,-, SnH, the magnitude of

11J("9Sn'H)( decreases with an increase in n from 1 to 3 as a result of the
greater electronegativity of the phenyl group as compared with an alkyl
group. These trends are very similar to those observed for the corresponding
s i l a n e ~ and
' ~ ~may be attributed to rehybridi~ation'~~
at the tin atom.
b. 'J( 1'9Sn'3C). Owing to the large number of organotin compounds
there is a wealth of 1J("9Sn'3C) data. Therefore, only a small fraction of the
results available can be addressed here. References 125-150 contain much
material and should be consulted in addition to the references given in the text
or in the tables for further information.
112 BERND WRACKMEYER

TABLE 10
Tin hydrides, tin eoordinrtion amber 34
Compound 61'9Sna Solvent Footnotes Reference

Me,SnH - 104.5 C6H6 9

( 1744) 119
Et,SnH -40.0 b 9
( 16I 3.2) 121
Pr",SnH -89 3
(1W) 294
Bu",SnH -91.4 279
( 1604.4) 295
-89 2
-95 37
Ph,SnH - 164.5 4
- I48 37
(1935.8) 296
Me,SnH, -225 10% CeH,,, -20°C 170
(1 797)
-229 - 3
Et,SnH, -231 80% C6H6 9
(1689.6) 20% C6H6 121
Bu,SnH, ( 1682) 122
Ph,SnH, -234 20% TMS 170
(1928) 2%
MeSnH, -346 60% toluene, - 35°C 258
(1852)
EtSnH, -282 50% in Bu",O 9
( 1790.4) C6H6 121
PhSnH, - 320 - 3
( 1920) 170
SnH, -500 - C 170
[SnH,I+ - I86 FSO,H, - 80°C 297
(2960)
~~

'Values 1J(119Sn1H)are given in parentheses.

Should be remeasured.
Extrapolated value, see Fig. 5.

The sign of lK(l19Sn13C) is negative in (CH,),SnLilS1 and may be

assumed to be positive in most other organotin compounds. In the case of
methyltin compounds, a plot of 1J(119Sn'3C) against zJ(119Sn1H)helps to
predict the magnitude of one or the other coupling. 5 1
Starting from tetramethylstannane, the replacement of a methyl group by
any other substituent causes significant changes in the magnitude of
1J"'9Sn13C(CH,)]. This is the result of the polarizability of the l19Sn
nucleus and can be ascribed to rehybridi~ation"~ at the tin atom. Within this
terminology the increase, or decrease, in 1J("9Sn13C) is attributed to the
 ''9Sn-NMRPARAMETERS 113

respective change in the "s character" of the Sn-C bond."2J53 In Tables 27

and 28, values of 'J"'9Sn'3C(CH,)] arecollated for the compounds Me,SnX
1
and Me,SnX,, respectively. In (alkyltrimethyl)stannanes, 1J("9Sn' ,C) is
roughly ~ o n s ta n t . " ~The situation becomes more complex in the case of
alkenyl ~ t a n n a n e s ~ ~and
* " the
~ relationship between 'J(' "Sn13C) and the
hybridization of tin and carbon atoms breaks down completely in al-
''-'
kynyltrimethylstannane~.~~*'5g With an increase in the number of
'
electronegative ligands the 9Sn nucleus becomes less polarizable and the
couplings, 1J('19Sn'3C), are more in agreement with the concept of the s
character of the Sn-C bond.
A typical example of this is found in the ratio of the following 'J(' 19Sn',C)
values corresponding closely to the ratio of the formal Sn-C s character (2.0)
in the case of X = Br, whereas this is not true if X = CH,:

X CH,-SnX, HCrC-SnX,
CH' -337.8"' -414.8"'
Br -640.0'60 - 1290.0'6'

The value of I'J(1'9Sn'3C)I in compounds of the type R4Sn (R = Me, Et,

Pri, Bun, Bu') decreases in magnitude with increasing chain length and
branching of the alkyl g r ~ u p . ' ~This ' ~ ~ that changes in the nature of
~ * shows
the Sn-C bond are sensitively reflected by 1J(1'9Sn'3C). The fairly small
values of I'J(' 'gSn'3C)I in allyl- and benzyltin compounds may be explained
in terms of 6-n c o n j ~ g a t i o n . ' ~ ~ J ~ ~
The loose relationship between 'J("9Sn'3C) and s character means that
interbond angles at the tin atom in cyclic compounds are important. This is
particularly noteworthy for the exocyclic I 'J(l 19Sn13C)(data which, in most
cases, are smaller in five- and four-memberedrings than in six-membered rings
or analogous noncyclic compounds.
The small values of I 'J(' 19Sn13C)( in cyclopentadienyltin(I1) com-
p o u n d ~reflect
~ ~ .the~ small
~ s electron participation in the cluster bonding, in
agreement with MO calculation^^^:

I J( I "Sn13C): BF4-

51.5 Hz
11.8 Hz
114 BERND WRACKMEYER

In conclusion, 'J(" 9Sn'3C) values obtained so far cover the range between
+ 220 Hz (Me,SnLi.3 HMPT) and - 1466 Hz [Cl,Sn(C-CH),]. The extent
of this range shows that this parameter is very useful as an analytical criterion
and in discussions of structure and bonding.

c. 1J(119Sn29Si), 1J(119Sn119Sn), and 'J( zo7Pb119Sn). As shown in

Table 21 there are only a few data available for 1J(1'9Sn29Si) and
1J(207Pb119Sn), whereas a great number of 1J(119Sn"9Sn) values have been
observed. The latter cover the enormous range between - 6000 and + 15,000
Hz. It is readily seen that small or even negative 'J("9Sn"9Sn) couplings can
be assigned either to anionic compounds (e.g., [(Me,Sn),Sn]-) or to di- or
polystannanes. The s overlap integral of the Sn-Sn bond is small in both types
of compound as a result of the weakness of the Sn-Sn bond, for steric
reasons, and because of the lone electron pair in the anionic compound.'66 All
this may lead to additional electronic excitations, of which some make
negative contributions to the mutual polarizability term nSnSn. The medium-
sized values of 1J(119Sn119Sn)(around +4000 Hz) are observed for
distannanes with methyl or phenyl groups attached to tin,'67 whereas very
large values of 1J(1'9Sn"9Sn) ( - 11,000 to 15,000 Hz) are found in ditin
complexes in which each tin atom gains a coordination number of f i ~ e . ' ~ ~ . ' ~ '
It is believed that two effects are mainly responsible for this unexpected
increase in the magnitude of 1J(119Sn119Sn):

1. The geometry at the tin atoms corresponds to trigonal bipyramids in

which the heteroatoms (0, S) occupy axial positions. This increases the s
electron participation in the equatorial positions, in particular in the Sn-Sn
bond owing to the greater electronegativity of carbon as compared to tin.
2. The electronegative atoms oxygen or sulphur linked to the tin atoms
greatly reduce the polarizability of the ",Sn nuclei. Therefore, negative
contributions to nSnSn,which may be of great significance even in
Me,SnSnMe,, are less likely to be important.

The 'I9Sn-NMR spectra of naked-metal cluster anions (Table 21) reveal

information on the number of tin atoms forming the polyhedron. Since these
compounds are nonrigid (relative to the NMR time scale), averaged coup-
lings 1J(119Sn"7Sn) are observed. The intensity and multiplicity of the "'Sn
satellitesshow the presence of [Sn,l4-" or [Sn4I2- .', Similar arguments lead
to the assignment of .[Sn,-,Ge,,]4-,82 whereas the existence of the corre-
sponding clusters [Sn, -,,Pb,,14- is demonstrated by the values of
'
'J( l 1 9Sn1.'7Sn) and J(207Pb"9Sn).80*81Furthermore, it is deduced that
alloys of the composition NaSnTl,,, give solutions in ethylenediamine (en)
containing the anion [Sn8T1]5-.82
 '9Sn-NMR PARAMETERS 115

The data available leave no doubt that l19SnNMR is an attractive tool for
the investigation of di- and polytin compounds. The trends observed, so far,
for 1J(119Sn119Sn)should also stimulate other spectroscopic studies in order
to base the interpretation of the NMR parameters on more firm ground. In an
attempt to find out whether the mutual polarizability term nSnSnor changes of
the valence s electron density [JI(0)z]are responsible for the large range of
1J(119Sn119Sn)data, Mossbauer isomer shifts [as a measure of I,~~.(O)~] have
been compared with 1J(119Sn119Sn)r e ~ u 1 t s . Although
l~~ this comparison
may be questionable from a theoretical point of view, it indicates that nSnSn
is
the major source of changes in the magnitude of 1J(119Sn119Sn).
' '' '
d. J( 9Sn 'B) . Except for J(205T1119Sn)in [(Me,Sn),Tl]Li ( - 11,610
Hz) and in [Sn,Tl]'- (800 Hz), all other one-bond "'Sn-Group I11 element
couplings concern 'J(' l9Sn' 'B) (Table 22). The comparison with analogous
values of J ( 'I9Sn' ,C) shows that the change in hybridization is much better
reflected by 'J(' 19Sn1'B) than by 1J(119Sn13C):

1J(119Sn11B)
(Hz) [Me&-BHJ: -554'* (Me,Sn),B-NMe,: -65715
1J(119Sn'3C)(Hz) Me,Sn-CH,: -338lS4 (Me,Sn),C=CH,: -298"'

Furthermore, the reduced couplings, 'K(119Sn1'B), are larger than

1~ ( 119Sn13C),although 11/13c(0)2 > 11/llB(0)2.
This is evidence for the influence
of the polar Sn-C bond on the mutual polarizability term nSnC.Since the
Sn-B bond is expected to be less polar, negative contributions to the contact
energy arising from bond polarity should be of minor importance.
Large values of the 1J(119Sn11B)couplings hamper the direct observation
of l19Sn resonances, in particular for trigonal boranes, because of the
broadening induced by scalar relaxation of the second kind (Section 111,B).
Since the couplings are so large, measurements at low temperature are not of
much help either. For rapid detection of the li9Sn resonances, and of the
l j( 119S.11 B) data, heteronuclear double resonance experiments (e.g.,
1~ { 119S }) are superior to l19Sn PFT NMR s p e ~ t r a . ' ~ - ' ~

So far, values of 1J(119Sn1'B)have been reported solely for Sn-B two

electron two-centre bonds. It would clearly be of interest to obtain
J(119Sn1'B) data for polyhedral cage compounds either containing the tin
atom or being attached to an organotin moiety. Both types of compound have
been ~ r e p a r e d ' ~ ' - but
' ~ ~no 1J('19Sn11B)values have been reported.
e. 'J("9Sn'5N) and 'J("9Sn3'P). Some 1J(1'9Sn'5N)data are given
in Table 29. The polarizability of the tin nucleus and the presence of the
nitrogen lone electron pair prevent, in general, the prediction of the sign and
magnitude of 1J(119Sn15N).In the case of multiple substitution it is
116 BERND WRACKMEYER

shown that 'K(' 19Sn15N) increases with increasing n in the series

Me,-,Sn(NMePh), (n = 1,2,3,4).Il8 This indicates that the polarizability,
'
which is large for small n, of the 19Snnucleus produces at least some of the
negative contributions to the contact energy in 19Sn-' 5N spin-spin
couplings.
Values of 'J("9Sn31P) are found, together with the d119Sn values, in
Table 20. Large negative contributions to the mutual polarizability term nSnp
in P(II1) organotin compounds are reflected by the large negative values of
1~ ( 119Sn31 P) [large positive 1J("9Sn31P)].'75 This mirrors the influence of

the phosphorus lone electron pair. As shown in the crystal structure of

dodecamethyl-113,413-diphospha-2,3,5,6,7,8-hexastannabicyclo[2.2.2]octane
' '' '
the bond angle Sn-P-Sn is 98" and J ( 9Sn3'P) is - 749 Hz, 76 which is
close to the value for (Me,Sn),P (- 832 Hz):

MezMe,

/sn-sn\
/ \
p Me Me,,P 1J(119Sn"P)= 749 Hz
\\Sn%n /
hn-sn /
Me,Me,

The values of 'K('19Sn3'P) become less negative if the phosphorus lone

electron pair is used in metal comple~ation.'~~*'~~*~~~ This trend is in
agreement with expectations based on the accepted theory of nuclear
spin-spin coupling.'7s However, it should be noted that values of
1K(3'P'3C) in analogous compounds are always positive. So far no sign of
'J(' "Sn3'P) has been determined in complexes of the type SnX,(PR,),, for
anions [SnX,PP,]- (X = halogen; see Table 20), or for phosphine complexes
of tin(II).59*92.'7 9
f. 'J( 'I9Sn 77Se) and 'J( '25Te119Sn).Data for the couplings
1J("9Sn77Se) and 1J('2sTe1'9Sn) are given, together with d"9Sn values, in
Tables 16-18. While the magnitude of 1J("9Sn77Se) in Sn(1V) compounds
does not change significantly,"' 'J("9Sn'2sTe) values appear to cover a
larger range. This is in agreement with the high polarizability of both Sn and
Te. Presumably, all values of 'K(119Sn77Se) and 'K('25Te''9Sn) are
negative.
In the cationic complexes of Sn(II),'81*182the presence of 'J('19Sn77Se)
shows that the exchange of the ligands ([PhSeI-, chex,P=Se; chex =
cyclohexyl) is slow compared to the NMR time scale. In these complexes
1 1J('19Sn77Se)lis much smaller than in the Sn(1V)-selenium compounds.
 ' 9Sn-NMR PARAMETERS 117

g. 1J(119Sn19F). There is only a single value of 1J(119Sn19F)(+2298

Hz) for a triorganotin fluoride (Table 11) in the 1 i t e r a t ~ r e . lAll
~ ~ other
l j 119 .19
( S F) data concern anionic complexes. For these an extensive list
is already a ~ a i l a b l e , ' ~with
~ . ~ most
~ ~ of the data taken from other
s o ~ r c e s . ~ Th
~ ~e -values
~ ~ ' of 1J("9Sn19F) of peroxo complexes of the type

TABLE 11

~~ ~~ ~~ ~ ~ ~ ~~ ~ ~

Compound a119Sn Solvent Footnotes Reference

(PhCMe,CH,),SnF + 139 cm, 183

Me,SnCl + 164.2 3-20% a.6 298
C6H6or
CHCI,
Et,SnCl + 155 30% CCI, b 271
Bu',SnCl +50 - 4
chex, SnCl +66.2 C6D6 b, c 76
CH,(SnMe,Cl), + 160.9 cM=I, 170
(PhCH,),SnCl +52 CDCl, a.6 1
Ph,SnCl -44.7 CDCl, a 299
Ph,@-CH,=CH-C,H,)SnCl -44.6 C6D6 d 286
(HC=C),SnCl -263.2 CDCl, 161
Me,SnBr + 128 3-20% a,b 298
C6H6 Or
CHCI3
Et,SnBr + 148 - b 277
Bu',SnBr +74.8 C6H6 4
CH,(SnMe,Br), + 137.6 CDCl, 170
Ph,SnBr -59.8 CM, 299
(HC=C),SnBr - 329.5 CDCl, 161
Me,SnI + 38.6 3-20% 298
C,H6 or
CHCl,
Bu',SnI +82.7 C6H6 4
Ph,SnI - 114.5 CCl, 279
- 112.8 CDCl, 299
Me,SnCl, + 137.0 30% CHzCl, a, e 8
+ 141.2 CCI,, saturated 35
Et,SnCl, + 121.0 30yo a.e 8
CCl,/CH,Cl,
But2SnCl , + 56 CCl, 67
(CH 2 1ISnCl2 - 114.2 CDCl, 286
(CH,=CH),SnCI, -40.9 - 278
Ph,SnCl, -32.0 CH,CI, 8
(pMe-C6H4) -21.1 C6D6 286
pCH,=CH-C6H,SnCl,
118 BERND WRACKMEYER

T A B L E 1 1 (cont.)
Compound 61'9Sn Solvent Footnotes Reference
(2-thienyl),SnCI2 - 38.4 CCI, 279
(HC=C),SnCl, - 194.5 CDCI, 161
Me,SnBr, + 70.0 3-2OYo 298
C,H, or
CHCI,
Et,SnBr, +96.0 20% CCl, 277
Bu', SnBr, i-76.5 Saturated C,H, 4
(CH,=CHCH,),SnBr, - 16.8 - 279
(HC=C),SnBr, -345.6 CDCI, 161
Me,SnI, -159 3-2OYo 298
C,H, or
CHCI,
MeSnCI, +21 3-20°h 298
C,H, or
CHCI,
- 15.2 5 M CCl, 35
EtSnCI, +6 30% CCI, 277
PhSnCI, - 63 CH,CI, 8
HC=C-SnCI, - 155 CDC1, 161
MeSnBr, - 165 3-200?' 183
C,H, or
CHCI,
EtSnBr, - 141 50% CC1, 277
HCEC-SnBr, -437.2 CDCI, 161
MeSnI, -699.5 Saturated CCI, 288

For other conditions see review 3.

For other compounds trialkyltin halides see review 3 and reference 383.
Width 45 Hz; according to 13CNMR it is a mixture of -93% all equatorial and
equatorial, equatorial chex,SnCI.
- 7% axial,

(p-Me-C,H,),(p-CH,=CH-C,H,), -,SnCI: 6'I9Sn, - 39.6, - 37.7.,",

For other dialkyltin halides see review 3 and references 373 and 374.
For other alkyltin halides see review 3.
For other aryltin halides see review 3 and references 369 and 382.
'Between - 150 and - 155, dependent on SnCI, concentration.

[SnF, -,, (00H),,]2- (n = 1 to 5 ) have been reported.' The replacement of

[OH]- by the [OOHI- group increases the value of 11J('19Sn19F)I,e.g.:

1J(119Sn19F)(Hz)

cis-[SnF,(OH),] '- ~is-[SnF,(00H),]~-*"

1820 (OH, trans) 2064 (OOH, trans)

1518 (F, trans) 1692 (F, trans)
 l19Sn-NMR PARAMETERS 119

TABLE 12
Tin halides, tin coordination number = 4

Compound 6' 19Sn Solvent Remarks Reference

SnCI, - 150 - *2 28 1
- 147.8 - 35
- 150.0 CSZ, -30°C 64
BrSnCI, -260 to -267 - 28 1
- 265 CSZ, - 30°C 64
ISnCl, -543 to -557 - 28 1
- 543 CSZ, -30°C 64
Br,SnCI, -384 to -386 - 28 1
- 382 CSZ, -30°C 64
BrISnCl, -663 to -672 - 28 I
- 663 CS,, -30°C 64
I,SnCl, -937 to -951 - 28 1
-927 CS,, -30°C 64
Br,SnC1 - 508 to - 509 - 28 1
- 502 CSZ, -30°C 64
Br,ISnCI -783 to -796 - 28 I
-783 CSZ, - 30°C 64
Br1,SnCI - I060 to - I068 - 28 1
- 1057 CSZ, -30°C 64
1,SnCI - 1330 to - 1347 - 28 1
SnBr, - 638 CS, *I 28 1
-631.6 3 MCS, 35
-623 CSZ, - 30°C 64
ISnBr, -913 to -919 - 28 1
-905 CS,, -30°C 64
I,SnBr, -1187t0 -1195 - 28 1
- 1I76 CS,, -30°C 64
1,SnBr - I447 to - 1449 - 28 1
- 1438 CSZ, -30°C 64
SnI, - I701 cs2 +2 28 1
- 1698.6 2 MCS2 35
- 1679 CS,, -30°C 64

h. 'J( 'l9SnM) ( M = transition metal). Spin-spin coupling between the

19Sn nucleus and transition metals, M, has recently attracted much
attention.Ia9 The bulk of the data concerns complexes with the M-SnCl,
moiety, produced by insertion of SnCl, into the M-Cl bond. The presence of
( S M) demonstrates the kinetic stability of the M-Sn bond. More
l j 119

recently, data have become available for the products of the well-known
oxidative addition of organotin compounds to platinum(0) c o m p l e x e ~ . ' ~ ~
Therefore, at least for platinum compounds, it is possible to compare a series
120 BERND WRACKWYER

of 1J(195Pt119Sn)
values:
l j( 1 9 5 Pt"'Sn) (Hz)

n=O 1 2

The trend of this and of most sets of data in Tables 24 and 25 is in accord with
expectations. The magnitude of 11J(195Pt1 19Sn))depends strongly upon the
polarizability of the lg5Ptnucleus, which in turn is partly a function of the
ligand trans to the stannyl group. Thus 1J(195Pt119Sn)lincreases with a
decreasing "trans effect." The magnitude of I1J(195Pt119Sn)lreflects to some
extent the energy of the Pt-Sn bond. Therefore, a crude relationship exists
between the Pt-Sn bond length and (1J(195Pt119Sn)1.192 It should be noted
that the SnCl, ligand is regarded as a weak t~ donor and a a acceptor. 193 The
balance of both properties will affect the magnitude of 'J('19SnM). In
particular, the occupation of Sn d orbitals by metal electron density may
influence lJ(l 19SnM), probably by reducing negative contributions to the
contact energy term.
Although there are only two values of 1J(199Hg119Sn) available so far,194
they support the argument that the polarizability of the metal plays a major
role. The polarizability of both mercury and tin is reduced by replacement of
the Me3SiCH, group with C6F, groups. This leads to an almost threefold
increase in the magnitude of 11J(119Hg119Sn)l:
'J( lg9Hg119Sn)(Hz)

(Me,SiCH,),Sn-Hg-Sn(CH,SiMe,), 6157"*
(C,F,)jSn-Hg-Sn(C,F,), 17,550'94

A more detailed discussion requires more data on M-SnX, com-

p o u n d ~ . ~ ' "It~is~ evident
~ that the nature of the transition metal-tin bond
depends, in a complex way, on various factors which may be reflected to some
extent by the magnitude of lJ(l 19SnM).However, experience with one-bond
couplings of large and polarizable nuclei shows that changes in the magnitude
of these couplings are difficult to predict and even more difficult to interpret.
On the other hand, this sensitivity may help in finding small differences in the
bonding situation and there is clearly a need for other physical methods to
prove this point when it arises from NMR measurements.

2. Geminal couplings, 'J(SnX)

The magnitude and sign of geminal couplings, 2J( 9SnX), depend (1) on
the intervening atom Z, (2) on the nature of the substituents on tin, on the
 9Sn-NMR PARAMETERS 121

TABLE 13
Neutral d a n i d complexes of tin halides and organotin h a l i w b tin coodinah number 3 4

Compound 6119Sn Solvent Footnotes Reference

Me,SnCl-DMSO +3 DMSO C 88
Me,SnCI-HMPT -47.5 10% HMPT C 4
Me,SnI-DMSO +6.5 DMSO 4
Et,SnX-Imidazoles d CDCI,, -60°C d 53

-51.1 259

Ph,SnCl-DMSO -226.8 DMSO C 66

Ph,SnCI-HMPT -238.9 CDCIJHMPT C 66
Ph,SnCI-pyridine -203.5 Pyridine 66
Ph,SnBr-DMSO -228.4 DMSO C 66
Ph,SnBr-HMPT -239.6 CDCl,/HMPT C 66
Ph,SnBr-pyridine -224.5 Pyridine 66
Ph,SnI-DMSO -228.5 DMSO C 66
Ph,SnI-pyridine -236.3 Pyridine 66
Me,SnClz (DMSO), -246 DMSO 88
Me,SnI, (DMSO), -315 DMSO 4
MeSnC1, (DMSO), -457 DMSO 88
MeSnI, (DMSO), -795 DMSO 4
MeSn(OH)C12(H20)2 -487 H,O 61
trans-[L,SnCl,] -700 CHZCI,, -30°C e 65
-622 CHZCI,, - 100°C f 65
trans-[L,SnCl,Br] -871 CHZCI,, -30°C e 65
tram-[L,SnCl,Br,] - 1048 CHZCI,, -30°C e 65
(Cl, Cl-trans)
trans-[LzSnCl,Br,] (Br, Br-cis) - 1053 CHzCl,, - 30°C 101
tram-[L,SnClBr,] - 1260 CHZCl,, -30°C 101
tram-[L,SnBr,] - 1479 CHZCI,, -30°C 65
- 1367 CHZCI,, - 100°C
cis-[L,SnCI,] -707 CHZCl2, -30°C 65
-632 CHZCI,, -30°C 65
cis-[L,SnCI,Br] (Cl, C1) -881 CHZCl,, -30°C 65
-790 CHZCl,, -30°C 65
cis-[L,SnCI,Br) (Cl, Br) -887 CHZCl,, -30°C 65
-813 CHZCI,, - 100°C 65
cis-[L,SnCl,Br,] (Cl, Cl) - 1040 CHZCI,, - 30°C 65
-958 CHZCl,, -30°C 65
cis-[L,SnCl,Br,] (Cl, Br) -988 CHZCl,, - 100°C 65
cis-[L,SnClBr,] (Cl, Br) - 1248 CHzCl,, -30°C 65
-1170 CHzCl,, - 100°C 65
cis-[L,SnCIBr,] (Br, Br) -1190 CHZCl,, - 100°C 65
122 BERND WRACKMEYER

TABLE 1 3 (cont.)
Compound 6"9Sn Solvent Footnotes Reference
cis-[L,SnBr,] - 1383 CHZCI,, - 100°C f 65
SnF, -629.0 0.462 M DMSO c, h 5,300
-626.1 1.58 M HMPT c,h 5,300
SnCI, -260.3 2.6 M h 5.300
dimethoxyethane
- 324.1 0.74 M DMF c, h 5,300
- 358.2 1.09 M DMSO c, h 5,300
- 285.2 1.7 M HMPT c, h 5,300
- 236 THF C 28 1
-238 THF/C6D6 C 56
SnBr, - 72.3 0.39 M h 5,300
dimethoxyethane
- 70.7 THF, C,D, C 56
- 202.1 0.32 M DMF c,h 5,300
-319.5 1.3 M DMSO c, h 5,300
SnI, - 152.6 5.117 M DMF c, h 5,300
- 586.0 1.29 M DMSO c,h 5,300
- 174.4 1.24 M HMPT c, h 5,300
[Ph,SnBr,]- - 239.6 0.26 M CD,NO, 66
-231.5 0.15 M DMSO C 66
[MeSnCl ,] '- -464 HZO i 8
[MeSnBr,]'- -662 HZO I 8
[Ph,SnCI,]- - 257.2 0.62 M CD,NO, 66
[SnF,]'- - 888 HZO 8
[SnF,C1]2- -826 HZO 4
[SnCl,]'- -732 CHZCI,, -30°C 64
[SnCI,Br-]2- -912 CHZCI,, -30°C 64
tran~-[SnCI,Br,]~- - 1092 CHZCI,, -30°C 64
~is-[SnCl,Br,]~- -1115 CHZCI,, -30°C 64
mer-[SnCI,Br,lZ- - 1322 CHZCIZ, -30°C 64
fa~-[SnCl,Br,]~- - 1336 CHZCI,, -30°C 64
tran~-[SnCl,Br,]~- - 1548 CHZCI,, -30°C 64
cis-[ SnCI, Br,] - - 1559 CHZCIZ, -30°C 64
[SnCIBr,12- - 1800 CHZCI,, -30°C 64
[SnBr,]'- -2064 CHZCIZ, -30°C 64
[SnCI,L]- -700 CHZCI,, -50°C e 65
- 668 CHZCI,, - 100°C f 65
[SnCI,BrL]- (Cl) -880 CHZCI,, -50°C e, g 65
- 841 CHZCI,, - 100°C f>g 65
[SnCI,BrL]- (Br) -883 CHZCI,, -50°C e, g 65
-880 CHZCI,, - 100°C fx 65
[SnCI,Br,L]- (CI-trans) - 1053 CHZCIZ, -50°C e, g 65
- 1033 CHZCI,, - 100°C fx 65
[SnCI,Br,L] (CI-cis) - 1073 CHZCI,, -50°C e9 g 65
- 1033 CHZCIZ, - 100°C Lg 65
 I9Sn-NMR PARAMETERS 123

T A B L E 13 (cont.)
Compound 6119Sn Solvent Footnotes Reference

[SnCI,Br,L]- (Br) - 1080 CHZCIZ, -50°C 65

- 1033 CHZCIZ, - 100°C 65
[SnCI,Br,L]- (Cl) - 1270 CHZCIZ, - 50°C 65
- 1236 CHZCIZ, - 100°C 65
[SnCI,Br,L]- (Br-trans) - 1283 CHZCIZ, -50°C 65
- 1236 CHZCIZ, - 100°C 65
[SnCI,Br,L]- (Br-cis) - 1284 CHZCIZ, - 50°C 65
- 1236 CHZCIZ, - 100°C 65
[SnCIBr,L]- (Cl) - 1501 CHZCIZ, -50°C 65
- 1451 CHZCIZ, -50°C 65
[SnCIBr,L]- (Br) - 1501 CHZCIZ, -50°C 65
- 1451 CHZCIZ, - 100°C 65
[SnBr,L]- - 1737 CHZCIZ, -50°C 65
- 1679 CHZCIZ, - 100°C 65
[SnCIJ - 30 CHZC1Z/C6D6 56

a For complexes with PR, see Table 20.

* For more ~ 5 " ~ Sdata
n see reviews 1-4 and references 367 and 383-385.
DMSO, Dimethyl sulfoxide; HMPT, (Me,N),P=O; DMF, dimethyl formamide; THF,
tetrahydrofuran.
No reference is given for the 6119Sndata; the 6"'Sn values for Et,SnX (X = CI, Br, I) do not
agree with literature data; there is a shift to lower frequency of the "?Sn resonance in the presence
of 1-ethyl and 1-vinylamidazole, indicating coordination number 5 for the tin atom. Various
isomers are claimed to be present.
L, Bu",P=O; zJ('1gSn031P)vanes between 130 and 230 Hz.
f L, Acetone.

I ) The group trans to the L groups is indicated in parentheses.

119Snresonances shift to higher frequency on dilution.300

S1I9Sndepends on pH.
j Counterion is (Bu',PH]+.

intervening atom Z, and on X, (3) on the Sn-Z-X bond angle, and (4) on the
stereochemistry of the rest of the molecule with respect to the SnZX fragment.
The complex behaviour of 'J('19SnX) is best illustrated by considering the
absolute values of 12J("9Sn"9Sn)l, which range between 0 and 35000 Hz;
'J("9Sn"9Sn) may be of either sign. This situation may be somewhat
discouraging at first sight but it has stimulated much work in the area of
geminal tin couplings. Thus, a qualitatively useful picture slowly emerges
which enables one to use these parameters as a diagnostic tool without
attempting a quantitative theoretical analysis. A useful concept, to rationalize
geminal couplings in terms of the contact energy, divides the contributions
into three parts.195These describe the nature of the Sn-Z bond and the nature
of the Z-X bond with respect to the transfer of nuclear spin information
 124 BERND WRACKME=

TABLE 14
Orgawtin hydroxides, &oxides, and related c o m p o tin
~ coordination number 3 4
~~ ~~~~~~~~

Compound 6119Sn Solvent Footnotes Reference

Me,SnOH +118 Saturated CH2C12 b 301
Ph,SnOH - 86 CH2C12 183
-82.5 CDCl, 299
Me,SnOMe + 129 Saturated C6H6 b 51
Me3SnOPri + 109 50% C6H6 51
Me,SnOBu' +91 50% C6H6 b 51
Me,SnOPh + 134.3 C6H 12 b 302
Me&-Ox +41.8 - c, d 69
Me,SnOSiPh, + 121 Saturated CCI, I

+ 165.7 30% CDCl, 303

Et,SnOMe + 100.3 CH2C12 279

Et,Sn-Ox +28.5 CDCI, C 69
Pr",Sn-Ox + 34.9 CDCl, C 69
Bu,SnOMe +83 - 304
Bu,SnOEt +86 - 304
Bu,SnOPri + 16 - 304
Bu,SnOBu' +60 - 304
Bu,SnOPh + 105 - b 304
Bu",Sn-Ox +30.1 - c 69
OMe
I

+99.0 Toluene e 250

Me
Bu",SnOOBu' + 105 CH2C12 8
Bu",SnOP(S)(OMe), +68.4 C6D6 305
Bu",SnOSiMe, +71 - 304
Bu",SnOSiPh, + 89 - 304
(PhCH,),Sn-Ox -98.2 CD2C12 c 69
Ph,Sn-Ox - 190.5 CDCI, c 69
- 1.92 30% CHCI, 58
- 190.1 CDCl, 66
Ph,SnOOBu' -91 CHZCl2 8
Ph,SnOSiPh, - 103 CH2C12 8
Me,Sn(OMe), - 126.3 C6H6 306
 "'Sn-NMR PARAMETERS 125

TABLE 14 (con?.)
Compound 6"9Sn Solvent Footnotes Referenoe

Me,Sn(OEt), - 125.9 C6H6 b 306

Me,Sn(OBu'), - 1.8 - 51
Me,Sn(OSiPh,), + 2.0 CH,CI, 8
Me,Sn(Ox), -237 20% CHCI, C 58
Me2Sn(2-Me-Ox), -228 8% CH,CI, C 58
-235.8 CDCl, 69
Me,Sn(acac), -365 15% CHCI, f 57,58
Me,Sn(bzac), - 356 15% CH,CI, g 58
Me,Sn(dbzm), - 348 20% CH,CI, h 58
Me,Sn(trop), - 197 20% CH,CI, i 58
Me,Sn(koj), - 174 20% DMSO i 58
Et,Sn(OMe), - 181 - 217
- 165 10% C,H, 277
Et,Sn(OBu') , -31 277
Et,Sn(Ox), -264 25% CHZCI, c 277

Et,Sn'O] - 177 277

O
\
Bu",Sn(OMe), - 159 b 3
Bu",Sn(OEt), - 154 b 1
Bu",Sn(OBu'), - 34 b 304
Bu",Sn(OPh),. - 138 b 304

- 189 Saturated CHCI, b 304

71

-PY - 144 CDCI, 71

-dmf - 137.2 CDCI, 71
-dmso - 144 CDCI, 71

BunzSn'oy - 164 Saturated CHCI, 304

71

rpy
'
0

Bu",Sn'o - 146.4 CDCI, 71

'
0
 126 BERND WRACKMEYER

T A B L E 14 (cont.)
Compound bLL9Sn Solvent Footnotes Reference

- 155 Saturated CHCI, 304

71

- 145.6 CDCI, 71
- 144.9 CDCI, 71

Bu'',SY]
'
0 - I54 50% CCI, 1

-154.5 CHCI,, pyridine, k 245

1 ~ 1 ,-40°C

-216 CHCI, 307

Bu",Sn(Ox), -262 30% CHCI, 58

Bu',Sn(OMe), - 114.7 - 4
Bu',Sn(OEt) , - 123.4 Neat, 60°C 3
Bu',Sn(OCH,CH,),NR
R
-
H -209.5 CH,Cl,, 32°C rn 52
-210.5 Acetone-d, , 32°C
Me -205 CH,Cl,, 32°C m 52
-204 Acetone-d,, 32°C 52
Bu',Sn(acac), -486 CCI, f 67
Bu',Sn(trop), - 326 CCI, i 67
Bu',Sn(Ox), - 338 CCI, c 67
-341 Saturated C,H, 4
Bu',Sn(2-Me-Ox), -311 CCI, c 67
Ph,Sn[OP(S)(OPh),l2 + 58.9 CDC1, n 305
Ph,Sn(OSiPh,), -188 CDCI, 1
Ph,Sn(Ox), - 397 15% CHCl, c 58
Ph,Sn(acac), -514 30% CHCI, f 58
MeSn(OEt), -434 50% mesitylene b 51
MeSn(0Bu') , - 177.2 - b 51
 "Sn-NMR PARAMETERS 127

T A B L E 14(cont.)
Compound 6119Sn Solvent Footnotes Reference

MeSn(OCH,CH,),N - 556.7, CHCI,, -40°C 54

-380.7, 55
- 375.4
Bu"Sn(OEt), -432 16% C6H, b 98
Bu"Sn(OBu'), - I99 12% C,H, b 98
Bu"Sn(0CH ,CH,) ,N - 559, CHCI,, -40°C 0,P 54
- 382.9, 55
-375.9
Bu"Sn(Ox), -561 10% CHCI, c 57
Bu'Sn(OCH,CH2),N - 246.4 CHCI,, -50°C 54
55
-245.5 CHCI,, + 2 7 T 54
PhSn(OCH,CH,),N -620.5 CHCI,, -40°C 54
-443.4, 55
-433.2
o-Me-C,H,Sn(OCH,CH,),N - 287 CDCI, 55
Bu",Sn(Cl)Ox -112 30% CHCI, 58
Ph,Sn(Cl)Ox -245 20% CHCI, 58
Bu"Sn(Cl)(Ox) , - 395 30% CHCI, 58
[Bu"Sn(Ox),],S -333 15 Yo CHCI, 58
~~

(1 See also review 3 and references 383-389 for further 611'Sn data.
* For other conditions see review 3.
Ox, Oxinate.
6'19Sn values in CD,CI,, +50.5; CDCI,, +50.9; C,D,, +47.8; CD,OD, +42.8 (and another broad
signal at + 65.8).
For more 6"'Sn data of Bu",Sn ethers of carbohydrates see reference 250.
acac, Acetyl acetonate.
@ bzac, Benzoyl acetonate.
dbzm, Dibenzoyl methanoate.
trop, Tropolonate.
j koj, Kojate.

-
In reference 308 6"'Sn values are given for Bun& derivatives of diols with a carbohydrate structure;
range of 6"'Sn is - 120 to - 180 ppm, indicating dimeric structures; see also references 250,309.
' Oligomers of the type [(Bu",SnO),O],C,Ph, show 6"'Sn values from ca. - 193 to -275.,1°
6"'Sn shifts to lower frequencies(3-4 ppm) at -40"C.52
" This may be Ph,Sn[SP(O)(OPh),], considering the 6"'Sn value.
For other conditions, see references 54,55.
P These stannatranes have a trimeric s t r u c t ~ r e . ~ ~ . ~ ~
128 BERND WRACKMEYER

TABLE 15
Orgnnotin carboxylates and thiacarboxylates,~tin coordination number 3 4

Compound 6119Sn Solvent Footnotes Reference

Me,SnOC(O)H + 2.5 3 M CDCl, 183

+ 150 0.05 M CDCI, 183
Me,SnOC(O) Me + 129 Saturated CDCl, 3
Et,SnOC(O)Me + 102.4 CH,C1, 279
Bu",SnOC(O)Me +96 CH,CI, 8
Ph,SnOC(O)H -91.4 Saturated CDCI, 72
Ph,SnOC(O)Me - 121 <0.5 M CDCI, 183
- 113.7 CDCI, 72
Ph,SnOC(O)Et - 121.0 <0.5 M CDCI, 183
- 114.0 CDCl, 72
Ph, SnOC(0) Bu' - 117.7 CDCl, 72
Ph, SnOC(0)Ph - 109.9 0.56 M CDCI, 66
Ph,SnOC(O)CF, - 64.4 0.48 M CDCl, 72
-65.1 CDCI, 183
Ph,SnOC(O)CH $1 -95.0 <0.5 M CDC1, 183
-89.8 Saturated CDCI, 72
Ph,SnOC(O)CHCI, -79 <0.5 M CDCI, 183
-75.7 Saturated CDCI, 72
Ph,SnOC(O)CCI, -80.0 5 CDCI,
~ 0 .M 183
,
Ph, SnOC(0)CH Br -91.1 Saturated CDCI, 72
Ph,SnOC(O)CHBr, - 77.5 Saturated CDCI, 72
Ph,SnOC(O)C,H,-p-NH, - 122.6 0.55 M CDCI, 66
Ph,SnOC(O)C,H,-o-NH, - 116.8 0.41 MCDCl, 66
Ph,SnSC(S)NEt, - 189.8 0.43 M CDCI, 66
- 191 30% CDCI, 58
- 194.5 CH,CI, 2
Me,Sn[OC(O)Ph], - 125 25% CHCI, 58
Me,SnSAB - 150 25% CH,CI, b 58
Bu",Sn[OC(O)Me], - 195 - 28 1
Ph,SnSAB - 329 20% CHCI, b 58
Me,Sn[SC(S)NMe,], -338 30% CHCl, 58
M%S~[SC(S)N(CHZ)~]Z -310 CH,Cl, 2
Me,Sn[SC(S)NEt,], -333 30% CHCl, 58
-336 CH,Cl, 8
Bu"zSn[SC(S)N(CHz),]z -313 CH,Cl, 2
BU",S~[SC(S)N(CH,P~)~]~- 340 CH,CI, 2
Bul,Sn[SC(S)NMe,], -255 CCl, 67
Bu',Sn[SC(S)NEt,], - 262 CCl, 67
Ph,Sn[SC(O)Ph], - 101.2 CHCI, 278
Ph,Sn[~C(S)N(CH,),I, -481 CH,Cl, 2
Ph,Sn[SC(S)NEf,], -501 30% CHCI, 58
Ph,Sn[SC(S)N(CH,Ph),], - 490 CH,CI, 2
PhSn[SC(S)NMe,], -695 5% CHCI, 57
 ''9Sn-NMR PARAMETERS 129

TABLE 1 5 (cont.)
Compound 6119Sn Solvent Footnotes Reference

Me,Sn(CI)[SC(S)NMe,] -204 30% CHCI, 58

Me,SnX[SC(S)NEt,]
X
- -201 30% CHCI, 58
C1 -204 CH,CI, 8
Br -233 CH,CI, 8
I -292 CH2CI, 8
PhSnCI[SC(S)NMe,], - 361 10% CHCI, 57,58

For 61L9Sndata of other organotin carboxylates and thiocarboxylates see review 3 and
reference 390.
SAB, Dianion of N-(2-hydroxyphenyl)'salicylaldimine.

TABLE 16
Organotin thiolates and selenolntes," tin coordination amber 34
Compound 6 '"Sn Solvent Footnotes Reference

Me,SnSMe +90 298

Me,SnSEt + 78 88
Me,SnSBu' + 55.5 88
Me,SnSPh +90.5 88

R=Me + 191.9 CDCl, 235

+ 59.4 DMI c 235
R=Bu' + 179.6 CDCl, 235
+96.1 DMF c 235
Ph,SnSMe -47 30% CHzCl, 288
Ph,SnSBu' - 84.2 30% CHZCI, 288
Me,SnSeMe +45.6 180
Me,SnSePh + 55 180
Ph,SnSeMe -69 Saturated CH,CI, 180
Me,Sn(SMe), + 144 3-20% C,H, or CHCI, b 298
Me,Sn(SEt), + 127 88
Me,Sn(SBu'), + 75 88
Me,Sn(SPh), + 122.5 Neat, supercooled b 88

Me,Sn"] + 190 Dilute CH,CI, b 89

-72.6 Dilute DMSO b, c 89
S'
 T A B L E 16 (cont.)
Compound 6”’Sn Solvent Footnotes Reference

+149 Dilute CH,CI, 89

Me,Sn”)‘S
-56.1 Dilute DMSO C 89

Me,Sn”] +231.0 CDCI, 76

‘S
Et,Sn(SMe), + 140 20% CCI, 277

Et,Sn”] + 199 20% CHZCI, + CDCI, 277

\S
Bu“,Sn(SEt), + I23 b 1

Bun2Sn”] + 193 25% CDCI, 277

\S
Ph,Sn(SMe), + 38.5 30% CH,CI, 288
Ph,Sn(SBu‘), + 30.4 30% CH,CI, 288

Ph,Sn/g + 78 Dilute CH,CI, 89

- 67.7 Dilute DMSO C 89
\S

Ph,dS] + 28.5 Dilute CH,CI, 89

- 85.4 Dilute DMSO 89
\S

- 30 50% CDCI, 1

Me,Sn(SeMe), +57.1 - 180

Me,Sn(SePh), +54.1 Neat, supercooled 180
Ph,Sn(SeMe), - 20 30% CH,CI, 288
MeSn(SMe), + 167 3-20% C,H, or CHCI, 298
MeSn(SEt), + 144 - h 88
MeSn(SBu‘), + 65 - 88
MeSn(SPh), + 101.5 - 88
MeSn(SCH,CH,),N - 33.3 CDCI, 55
Bu’Sn(SCH,CH,),N - 9.9 CDCI, 55
PhSn(SMe), + 107 30% CH,CI, 288
PhSn(SBu’), +11 30% CH,CI, 288
MeSn(SeMe), + 14.8 - 180
MeSn(SePh), - 16.5 - 180
PhSn(SeMe), -21 30% CH,CI, 288
~

For more 6IL9Sndata of organotin thiolates and selenolates see revie. 3.

For other conditions see review 3.
DMF, Dimethylformamide;DMSO, dimethyl sulfoxide.
 l19Sn-NMR PARAMETERS 131

between the l19Sn nucleus (k119Sn) and X (k,). A third parameter, F,, as a
function of one- and two-centre exchange integrals, describes the transfer of
electron spin information between the respective geminal bonding orbitals.
These parameters are related as shown by Eq. (12).
2~
(119SnZX) = kllSSnkXF,

This comprises arguments 1-4 above. Since k119Sn or k, represents

interactions corresponding to the spin-spin coupling of directly bonded
nuclei, the sign of 'Kcan be predicted if the sign of F, is known. From various
sign determinations of 'K(l19SnX) it appears that F, is frequently negative
when the Sn-Z-X bond'angle is between 90 and 110" and becomes positive
when the Sn-Z-X bond angle exceeds 110". Exceptions to this may be found
if X carries a lone electron pair or pairs.
From the practical point of view, the most important geminal couplings
2J(119SnX) are those for X = 'H, 13C, 31P, or 117s119Sn,which are
considered in more detail below.
a. 2J(119Sn1H). There is a wealth of 2J(119SnC1H)data available, as
shown by Petrosyan." Therefore, no data are given here; rather, the general
trends are briefly outlined. Generally, the value of 2J(119Sn1H)Iin methyltin
compounds increases with the coordination number of tin and with an
increasing number of electronegative ligands at the tin atom. The sign of
ZJ (119S 'H) in methyltin compounds is positive in most cases [2K(119Sn1H)

has a negative sign!] except forMe,SnLi in THF or (Me2N)3P0.151If the

intervening atom is an sp3 hybridized carbon the behaviour of 2J(119Sn1H)
follows roughly the well-known pattern of 2J(HH), which has been
rationalized using MO t h e ~ r y . ' ~ ~ . 'Thus,
~' in Me,Sn-CH,-X,
2f1119Sn1H(CH2)]becomes more negative if X exerts a +Zeffect or provides
n-electron density, and it becomes more positive in the case of a -Zeffect.
_ _ _ _ ~ ~
~

Me,Sn-CH, Me,Sn-CH,-SnMe, Me,%-CH,-Ph Me,Sn-CH,-CI

2J(119Sn'H)(Hz) +54.0 +63.0 + 62.1 + 19.0

H-CH, H-CH,-Ph H-CH,-CI
2J('H1H) (Hz) - 12.4 - 14.5 - 10.8

The polarizability of the Sn-C, or of any Sn-Z, bond accounts for the
sensitivity of 2J(119SnZ1H)toward changes in the rest of the molecule.
Therefore, it is not surprising to find that zJ(119Sn1H) across an sp2
hybridized carbon atom is fairly large and negative198 [zK(119Sn1H)is
positive!], whereas the corresponding values of 'J(HH) are generally small
and of either sign. Again, the values of J2J(119Sn1H)Iincrease with the
 132 BERND WRACKMEYER

coordination number of tin and with the number of electronegative ligands,

e.g.:
*J('I9Sn'H) (Hz)
Sn (CH=CH,), -99.7'98

H\ ;H
,c=c \
C1,Sn C-OCH, - 263 136
\@+

In Me,SnPHPh a positive sign of 2J("QSnP'H) has been determined.lQ9

The magnitude of 2J("QSnPt'H) depends, in the usual fashion, upon the
ligands at the tin atom and upon the geometrical position,200cis or trans, for
the 'H relative to the '19Sn nucleus.

rrans-[PtH(SnCl,)(PPh,),1 rranr-[PtH(SnPh,)(Pche~,)~]
zJ('19Sn1H)(Hz): 174OZo1 104202

In conclusion,it should be noted that the pattern of valuess of 2J(1I9Sn1H)

is very similar to that for other 2J(M'H) couplings in which M = 2QSi,207Pb,
or '"Hg.
b. 2J(11gSn13C). Most of the known 2J("QSn'3C) data have become
available only since 1975. Sign determinations have been carried out for only a
few, but, important examples.

H,C\ /Et
Et,Sn-CH,-CH, Ph2Sn /c=c
Me,Sn 'BEt,

2J(1'9SnC'3C)(Hz): + 23.So3 +29.096 -7O.O2O4

Et,Sn-C=C-H Me,Sn-SnMe,-CH, (Me,Sn),N-CH,

zJ(119SnC13C)
(Hz): -64.7159 -- 56.0205 + 12.2204

2J(1'9SnZ1'C)(Hz): + 57.OZo4
This shows that there is a fairly large range (> 125 Hz) of 2J(1'QSn'3C)
values even in trialkyltin derivatives. The change of sign found for
'J' 19SnC'3C) corresponds to the observations made for 2J('3CC'H).206
 '9Sn-NMR PARAMETERS 133

As is shown later, the values and the signs of 2J("9Sn13C) are extremely
useful in understanding the 2J("9Sn1'9Sn) data. The values of
I2J[' "SnC(sp)' 3C(sp2)]1 in olefins are frequently close to zero and, therefore,
may be of either sign.
In five-membered cyclic organotin compounds the value of 2J(119Sn'3C)
reflects contributions from both geminal and vicinal couplings. This provides
an explanation for the sign96 and m a g n i t ~ d e ~of~ .the
~ ' ~2J(119Sn'3C)data
observed for these compounds.
There is clearly a need for further data, in particular for 2J("9Sn'3C)
values in transition metal complexes relating to coupling across the
meta1.126*208-210 Several values of 2J[119Sn13C(C0)] in carbonyl com-
plexes have been reported. In the distorted octahedral complexes cis-
(R,Sn),Fe(CO),, three values of 2J("9Sn'3C) have been observed in the
slow exchange limit,208*209 It appears from the averaged value, due to fast
exchange, that two couplings have the same sign and one sign is different.
From the intensity of the 117/119Snsatellites in the ',C-NMR spectrum, only
2J("9Sn13Ca") can be assigned with certainty. The critical dependence of the
magnitude of this coupling upon geometrical changes is evident by comparing
the values of 2J("9Sn'3C) above with those obtained for the analogous
ruthenium and osmium complexes (R = Me).208

R Me Et Pr Bu Ph CI

2J(I 9SnI 3C") (Hz) f101 98 97 96 112 235

trans- or (Hz) +65 62 65 61 80 170
T33 26 26 25 43 37

2J( I9Sn13C'q) (Hz)

M 'J( 9Sn 'C") (Hz) Irons cis

Ru 61 143 36
0s 54 118 40

Similarly, no clear pattern emerges so far for five-coordinate cobalt complexes

(CO),CoSnR, (R = Me, Bu, Bz, Ph, C1) for which in some cases different
134 BERND WRACKMEYER

values of 2J(119Sn13Cax) and 2J(119Sn'3Ceq) have been observed (between 68

and 105 H z ) . ' ~Values
~ for 2J(119Sn13C)
in a dianion and a monoanion have
been reported and, in both cases, cis geometry has been assumed.

CI
I
[Ci,Sn-PI-SnCi ,I- [(Ci ,Sn),Rh(CO), 1'-
I
C
Ill
0
' J ( I I9Sn' 'C) (Hz): 195.02" i31.8210

c. 'J( "9Sn "9Sn). The magnitude of the geminal couplings

2J(119Sn119Sn)is readily available from the lI9Sn-NMR spectra of the
relevant compounds. In addition to the l17Sn satellites [AX spin system
converted to 1J(119Sn119Sn) by multiplication with y(119Sn)/y(117Sn) =
1.04651 the l19Sn satellites (AB spin system) can be observed if the tin
atoms are in different chemical surroundings. The large range of
'J(' 19Sn119Sn)results has been mentioned already and there is clearly a need
to classify these data.
A first step in this direction requires a knowledge of the sign of
2J("9Sn119Sn). So far the sign of 2J(119Sn"9Sn) has been determined for
only four compounds; (Me,Sn),CH (-309 H z ) , ~ (Me,Sn),SnMe,
'~ ( + 763
H z ) , ~ O(Me,Sn),NN(Me)SnMe,
~ (-833 H z ) , ~ 'and
~ (Me,Sn),P (-331.4
Hz).~', The signs of other 2J("9Sn'19Sn) values can be deduced by
comparison with the known signs of 2J(119Sn13C) in analogous com-
p o u n d ~ If. ~an
~ ~Me,Sn group is replaced by a methyl group a linear
correlation between 2J(119Sn) and 2J(1l9SnI3C) emerges. This involves
coupling across Z = C, Sn, N, S. From this a positive sign for 2J(119Sn119Sn)
in (Me,Sn),SnEt is deduced showing the parallel trend for 2J(1 19Sn119Sn)
with Z = C or Sn.204

Me,Z(SnMe,), EtZ(SnMe,), Z(SnMe,),

z=c I9 - 230 - 325

2 = Sn + 763 + 259 f 20

An increasing number of Me,Sn groups on the central atom Z leads to

more negative contributions for 2J(119Sn1I9Sn).
In bis(triorgan0tin) oxides the geminal couplings 12J("9Sn"9Sn)l corre-
spond to linear arrangements, SnOSn (solid state), and it is concluded that the
 9Sn-NMR PARAMETERS 135

linear structure [(Bu',Sn),O, [(PhCH,),Sn],O] prevails in solution,214e.g.:

(Bu",Sn),O (Bu',Sn),O [(PhCH,),Sn],O (Ph,Sn),O

,J( I I9Sn' I9Sn) (Hz) 440 916 617 437

Comparison with data for sulphides, which all have a bent SnSSn fragment,
shows that these values of 12J(119Sn119Sn)llie in a narrow range,214e.g.:

2J('19Sn119Sn)(Hz) 218 230 222

On the basis of the relationship between 2J(119Sn119Sn) and zJ(119Sn13C),

a negative sign is likely for 2J(119Sn119Sn)in the s u l p h i d e ~There
. ~ ~ ~are no
2~ ( 119 S n13 C) data available so far to deduce a sign for the 2J(119Sn119Sn)

couplings in the oxides.

Strong intermolecular association of stannanes is indicated by the presence
of a geminal coupling across the oxygen atom [[MeSn(OCH,CH,),N],,
2J(119Sn119Sn)= 156 Hz].~' It should be possible to verify the ladder
structure of the 1,3-dihaIogeno-1,1,3,3-tetraaIkyldistannoxaneson the basis
of 2J(119Sn119Sn)data. However, so far only the 6119Sn values are
reported. 70
The most intriguing values of 2J(119Sn119Sn)are found when the
intervening atom is a transition metal (Table 25). Many trichloro-
stannate complexes have been studied by multinuclear reso-
nance.189-192,210,211.215-231 The values of ( 119Sn119Sn) can be obtained
from the 19Sn-NMRspectra, provided intermolecular exchangeof the SnCl,
groups is sufficientlyslow in comparison with the NMR time scale. At present,
no quantitative theoretical approach is available to explain the enormous
range of IzJ(119Sn119Sn)l,from several hundred to >35,000 Hz.la9
However, some trends are in nice qualitative agreement with the behavior
displayed, e.g., by 'J( ,'P3'P), as far as the geometrical dependence and the
dependence upon the metal itself are ~ 0 n c e r n e d . l ~ ~
In the [Pt(SnCI,),l3- anion an average value is observed for
zJ(119Sn119Sn)= 6520 Hz.2119217*226 Taking into account the various
known data for trans (2J(119Sn119Sn)l,cis IzJ(119Sn119Sn)l,and eq
I2(119Sn119Sn)l(in trigonal-bipyramidal Pt complexes) it appears that it is
necessary to assume like signs for trans ' J and eq ' J (probably positive) and
the opposite sign for cis 'Jin order to match the observed averaged value of ' 5
in the platinum-pentakis(trich1orostannate)trianion. All of these values of
2J(119Sn119Sn) show a strong dependence on geometry and on the very subtle
 136 BERND WRACKMEYER

effects exerted by other ligands:

chex
I
N
Ill
C
I ,,.SnC4
CI,Sn-Rh,
I SnCI,
C
111
N
I
chex
2 J ( I 19snlI 9Sn)(Hz): 2523''' 14,141222

(Hz):
2J(11ySn119Sn) 2601 2 2 4 36,286l9 18,66319'

Cod cod

CI,Sn/'[\P (@Me) 3 CI,Sn

SnCI,
I831 229 903229

It has been pointed out that there appears to be no relationship between

2J("9Sn119Sn) and 'J(M'19Sn) (M) = 195Pt, '03Rh).189*210This is not
unexpected considering the various contributions that arise in particular for
the two-bond coupling pathways (Section V,B,2).

d. 2J(119Sn3'P).Values of 'J(l19Sn3'P) are reported for various types

of compound where the intervening atoms are carbon, tin, oxygen, sulphur,
selenium and various transition metals. Examples are given below and in
Tables 24 and 25.

2J(119Sn3'P)(Hz)

Me,P=C(SnMe,), P(Me2Sn=SnMe2),P frans-[SnCl,{(MeO),P0),1 [CI,Sn-OPBu,]-

38.413, 93.0'76 195.0234 160.065

[Sn[XP(~hex),],]~': X = 0 S Se

237.0, 11.0, 27.0181

 '9Sn-NMR PARAMETERS 137

In the 1,l-dialkyl-3-phenyl-3-thio-1,2,3-stannathiophospholanesthe
values of 'J(' 19Sn3'P) must be regarded as arising from contributions from
'4'19SnCC3'P) and 2J(1'9SnS31P), for which different signs are
proposed.235
2J(119Sn31P)(Hz)

65.4 in CDCI,
R = R' = Me 97.1 in pyridine
/ \ / \
R' S Ph 104.8 in HMPT

The solvent dependence of 2J("9Sn31P) reflects the increase in coordination

number of the tin atom.
No sign of ' J ( l 19Sn31P)has been determined so far. However, the analogy
between 2J("9Sn31P), 2J(1'9Sn1"Sn), and 2J(3'P31P) in transition metal
complexes (Tables 24 and 25), as far as the geometrical dependence (cis, trans)
is concerned, suggests that at least the reduced couplings 2K(1'9Sn31P)and
2K(31P31P)(positive) for the trans coupling pathway have the same sign.'89
Owing to the large difference in magnitude between IzJ(1'9Sn3'P)I cis and
trans values, this parameter is valuable in the structural elucidation of
transition metal complexes containing stannyl and phosphine ligands.
e. Other geminal couplings, 'J(SnX). In the five-membered tin-tellurium
heterocycle, 2J("9Sn'25Te) has been observed168:
Me, Me,
Sn-Sn
\
2J(119SnSn125Te)
= 385 Hz

Me2
In polyfluoroorganotin compounds values of l2J(' 19Sn'9F)(range from
< 10 to ,200 Hz.121.184.236.237
Again, there are remarkable values of zJ(l19Sn'95Pt) and 2J(1'9Sn'99Hg)
in transition metal complexes:
A
Ph2P PPh,
I I
CI- Pt -Pt-SnCI, ,J( 195PtPt
I I9Sn):9670 HzZz5
I i
Ph2pvPPh,
PPh,
I ,\C'
CIHg-lr-SnCI, 2J('99HgIr119Sn):41.479
HzZz8
I.4
 138 BERND WRACKMEYER

TABLE 17
Organotin chalcogenides (Sn-X-Sn)," tin coordination number = 4

Compound 6'19Snb Solvent Footnotes Reference

+ 109.5 - 301
+ 110.6 lo%C6D6 76
+ 113.1 80% CHZCI, 30 1
+117.1 50% CHZCI, 30 1
+ 87.0 90% CHIClI 9
+ 86.2 CCI, 279
+ 77.8 - 3
+ 82 90% C6H6 8
+ 84.5 CCI, 279
+ 77.8 - 3
- 39.3 Saturated C6H6 4
+ 9.3 CDCI, 76
- 85.5 CDCI, 76
- 84.3 CDCI, 311
- 72.9 CDCI, 311
- 109 CH,CI, 8
- 125 CCI, 312
+ 86.5 20% CH,CI, 30 1
+ 93.9 CDCI, 313
+ 87.0 C6D6 76
+81.9 CCI, 279
+ 26.9 CDCI, 76
- 53.7 CDCI, 76
+ 125.6 CS, C 218
+ 128 C6H6 8
+ 128.6 Toluene/C6D6 3 14
+ 131.0 C6H6 168
+ 134 C6H6 168
+119 C6H6 168
+ 126.9 CCI, 279
+ 123 C6H6 168
+ 124.1 CDCI, 76
+ 16.8 CDCI, 76

Me Ph 139.1 (SnR'), CDCI, 76

15.9 (SnR,)
Ph Me 15.7 (SnR'), CDCI, 76
136.2 (SnR')
 119Sn-NMRPARAMETERS 139

T A B L E 17 (cont.)
Compound dl"Snb Solvent Footnotes Reference

R=Pr' + 89.9 (SnS,), CDCI, 315

+ 116.4 (SnS,)
R=Bu' + 84.1 (SnS,), CDCI, 315
+ 108.4(SnS,)
Me,Sn-SnMe,
/ \
S +44 (Sn) 168
s\ Sn
/
+ 176 (SnS)
C6D6

Me,
(Me,Sn),Se +44.5 (1060) 20% CHZCI, 30 1
12
+42.6 (1090) C6D6 76
+ 50.7 (nr) CDCI, 313
[(C6HSCH 2)sSnl ZSe -2.0 (1281) CDCI, 76
(Ph,Sn),Se -78.5 (1213) CDCI, 76
-76 (nr) CDCI, 313
(Me,SnSe), +42(1228) C6D6 168
(Ph,SnSe), -44 (1380) CDCI, 76
315

<
Pr', (a) Pr', - 320 (SnSe,) CDCI,
Sn -Se \ /Se-Sn, (1 5351,
Se /sn\ /
se (b) 87.1 (SnSe,) CDCI, 315
Sn-Se Se -Sn. [I236 (a),
Pr', Pr', 1339 (b)]
Me,Sn-SnMe, + 82 (Sn) C6D6 168
/ \ (1 263),
Se\ /
Se
Sn
+ 21 (Sn,)
Me, (992)

Me,
,X-Sn
Me,% \ 'Y
/
X-Sn
Me2
X Y
S Se + 134 (SnX,), C6D6 168
+ 84 (SnY) C6D6 168
(1238)
 140 BERND WRACKMEYER

TABLE 17(cont.)
Compound 611gSnb Solvent Footnotes Reference

Se S +34 (SnX,) C6D6 168

(1220),
+ 91 (SnY)
(1245)
(Me,Sn),Te -66.8 (1385) 80% CH,Cl, 301
- 59.3 (nr) CDCI, d 313
(Ph,Sn),Te - 143.2 (nr) CDCI, 313
(Me,SnTe), - 195 (3098) C6D6 168
Me,Sn-SnMe, - 164 (Sn) C6D6 168
/ \ (31591,
Te\ ,Te - 38 (Sn,)
Sn (2554)
Me,

>
Me,
,X-Sn
Me,Sn
h-sn y
Me2
X Y
S Te + 148 (SnX,), C6D6 168
- 32 (SnY)
(3198)
Te S -225 (SnX,) C6D6 168
(30211,
-9 (SnY)
(3278)
Se Te +55 (SnX,) C6D6 168
(1244, Se),
- 79 (SnY)
(1196, Se;
3174, Te)
Te Se -213 (SnX,) C6D6 168
(3049, Te),
- 64 (SnY)
(1211, se;
3220, Te)
-81, -128 C2H2CL e 70
+ 144 20% CH2Cl2 9

a For more data on organotin chalcogenidessee reviews 2-4.

* 'J(11gSn77Se)or 1J(119Sn12'Te)values given in parentheses.
For other conditions see review 4.
'nr, Not reported.
6119Sn(+4 ppm) reported relative to Me,SnCI,, 0.2 M in C,H,CI, [83/29]; calculated for this table
with 6119Sn (Me,SnCI,) = + 137.
 '"Sn-NMR PARAMETERS 141

TABLE 18
Ti ehdcogenides (Sn-x-)," tin Coordilution number 3 4

Compound 6"'Snb Solvent Footnotes Reference

- 590 HZO 281

-93 Toluene, C6D6 316
-221 C6D6 317
- 136 ? 317
- 339.5 Toluene, C6D6 316
-899 soz,-60°C d 181
-720 so,, -60°C d 181
- 303 CD,CI, 68
-314 CDZCI, 68
+ 160 50% CHZCIZ 88
+ 165 3-20% C6H6 298
or CHCI,
+ 165 - 288
Sn(SEt), + 138 88
288
Sn(SPr'). + 106.5 88
288
Sn(SBu'), +26.0 Saturated CH,Cl, 88
288
Sn(SCH,Ph), + 132.0 25% CCI, 288
Sn(SPh), +44 Saturated CH,Cl, 88
288
(MeS),SnSBu' + 127 15% CHZCIZ
(MeS),Sn(SBu'), +92 15% CHZCIZ
MeSSn(SBu'), +58 15% CHZC12 288
(MeS),-,SnSCH,Ph, + 130 5% CH,Cl, 288
(n = 0,1,2,3) to +160
(MeS),SnSPh + 131 15% CHZCI,
(MeS),Sn(SPh), + 104 15% CHjclz 288
MeSSn(SPh), +77 15% CHZCI,
(Bu'S),SnI -210.5 30% CHZCI,
(Bu'S),SnI, - 565 30% CHZCI, 288
Bu'SSnI, - 1065 30% CHZCIZ
CSn(SBu'),I, +77.7 TOlUene/C6D6 318
+63.2 Toluene/C,D,/THF
Sn(SCH,CH,),PBu' -238 C6H6 59
(903,3'P)
CSn(SPh),l- + 125 CDSOD, -75°C 319
+ 140 CD,OD, + 2 2 T 182
[Sn(SPchex,),] '+ +94 so,, -60°C d 181
[Sn(SPh),SePh]- + 150 CD,OD, -75°C 182
[Sn(SPh)(ScPh),] - + 170 CD,OD, -75°C 182
[Sn(SPchex,),(SePchex,)] '+ + 133 so,, -60°C d 181
[Sn(SPchex,)(SePchex,),1 ,+ + 161 so,, -60°C d 181
(650)
 142 BERM) WRACKMEYER

T A B L E 18 (cow.)
Compound 6119Snb Solvent Footnotes Reference
Sn(SeMe), -80.5 - 180,288
(1 520)
Sn(SeBu'), - 262 Saturated CH,CI, 288
Sn(SePh), - 135 Saturated CH,CI, 288
(MeS),SnSeMe + 101 20% CH,CI,
(MeS),Sn(SeMe), + 43 20% CH,CI, 288
MeSSn(SeMe), -21 20% CH,CI,
(MeS),SnSeBu' + 80.6 30% C6D6
(MeS),Sn(SeBu'), - 18.2 30%C6D6 288
MeSSn(SeBu'), - 129.5 30% C$6
(MeS),SnSePh + 87 40% CH,CI,
(MeS),Sn(SePh), + 12.5 40% CH,CI, 288
MeSSn(SePh), - 61 40% CHZC12
[Sn(SePchex,),] + 181 so,, -60°C d 181
(570)
[Sn(SePh),]- + 184 CD,OD, -75°C 182
(710)
+ 207 CD,OD, + 2 2 T 182
[SnTe4l4- - 1828 Ethylene C 82
(2804) diamine

a See also reviews 2 and 4 and, in particular, references 288 and 391-393.
* Values of 1J(119Sn77Se) and 1J(119Sn125Te) are given in parentheses.
6119Snvalues given as -598 ppm relative to [Sn914- for which a 6119Snvalue (-1230) relative to
Me,Sn was reported.''
Referencingis not clear; 6lI9Sn [Sn(AsF6),(S02, -6O"C)I is given as +(?)1898 relative to Me,Sn; shifts
in this table are given relative to Me,Sn using the data in reference 182.

3. Vicinal couplings, 3J(SnX)

There are numerous values of 3J(119SnX)known for various X nuclei
although, at present, the main interest is probably focused on X = I3C. In the
case of X = 'H, a K a r p l ~ s - t y p edependence
~~~ may eventually emerge. This
dependence is also readily shown by the values of 3J("9Sn'3C 1.239 It is
expected that the dependence of 3J(119SnX)on the dihedral angle will be the
subject of further studies when more data for other elements for X become
available. In any case, the treatment of all 3J(119SnX)data is confined strictly
to empirical use considering the complex situation involving the charge
distribution in three bonds, the large polarizable "'Sn nucleus, the properties
of the X nucleus, and the various geometrical parameters (bond length, bond
angles, and dihedral angles).
a. 3J(ff9SnfH). A negative sign for 3J('19Sn'H) [positive sign for
3K(119Sn1H)!]has been observed in all cases where it has been determined.
 1 1 9 S ~ - N M RPARAMETERS 143

Many of these data have already been reviewed." In most cases it holds that
13J('19Sn'H)I > 12J("9Sn'H)I. Except for some representative examples for
ethyltin and tert-butyltin compounds, there have been only a few attempts to
use the values of 3J(1'9SnCC1H) is alkyltin compounds. This is partly a
consequence of the complex 'H-NMR spectra, which may lead to a similarly
'
complex pattern of 7/1 19Sn satellites that, in general, requires computer-
assisted spectral analysis. Although it is possible, in principle, to obtain many
of these data from lI9Sn-NMR spectra ('H this has not attracted
much interest so far. The values of J3J(1'9Sn'H)I decrease in magnitude when
the carbon atom, linked to tin in the coupling pathway 1'9Sn-C-C-1H, is
replaced by a heteroelement, either electropositive,e.g., Si, Sn, or Pb,12*13 or
electronegative, e.g., N, S , or Se.88,127*'80Interestingly, the course of
hydrostannation is readily shown using R,Sn-'H compounds. By observing
the 'H decoupled 'I9Sn-NMR spectra, the couplings 3J(119Sn2H)are
resolved and the stereochemistry is deduced from the relative magnitude of
( s HI.
3J 119 n2 87,101,102

There are plenty of data available for spin-spin coupling between the I9Sn
nucleus and olefinic protons. In most cases these data are readily obtained
from routine 'H-NMR spectra and their diagnostic value is highly
appreciated:

I 3J(1 9Sn'H) Jtrans> 1 3J('I9Sn'H) Jcis x I'J(' 9Sn'H) I

Similar to the behaviour of 3J(HH)cis,trans,an increase in
1 3J(119Sn'H)~cis,trans
is observed when electropositive substituents are at-
tached to the olefinic carbon atom:

Me,%, ,H 3J(''9Sn'H): cis 124 H P '

,c=c trans 208 HzZ4'
Me& 'H

Me,Sn
mE I9Sn I H),,,J Hz)'~' E
u './(I

154.0 BNEt,
127.0 CMe,
160.6 SiMe,
174.8 SnMe,

b. 3J( "'Sn J3C). The magnitude of the vicinal coupling, 3J(1'9Sn13C),

across a C-C single bond is related to the dihedral angle 4 between 'I9Sn and
I3C by a Karplus-type d e p e n d e n ~ e , '54*238~239.243.244
~~,~ provided that all
values of 13J(1'9Sn'3C)I have the same relative sign, which is likely to be
negative [thus 3K(119Sn13C)is positive]. Examples for 3J("9Sn'3C) are given
 144 BERND WRACKMEYER

in Table 30, and the relationship between 3J("9Sn'3C) and 4 is depicted

graphically in Fig. 8.
Similarly, it has been observed that 13J(119Sn'3C)ltrans
> 13J(119Sn13C)lcis
in olefinic compounds.g0However, the magnitude depends critically upon the
nature of the substituents:

'4 19Sn''C)
H-BEt,
HUH
Me+ -13CH3 Me,Sn -' 'CH,Me
Me,SnA1'CH3 Me& -' 'CH,Me
HUL3CH3 Me& -H H -"CH,Me Me,Sn -BE,,

Me3SnnH Me,Sn -BEt,

trans 77.890 106.0241 83.OZ4' 141.5246
cis 49.390 79.OZ4' 64.324' 118.2246

Similar to the case of 3J("9Sn'H), an increase in the magnitude of

13J(119Sn13C)Iis observed in the presence of electropositive substituents at
the C=C double bond.

b
-70

-80
[Hzl

-58

-40

to dihedral angle 4
I . . . . . . . . I . . . . . . . . I
0 50 90 130 180
FIG. 8. Relationship between the dihedral angle 4 and 3J(119Sn1'C). The numbers
correspond to the entries in Table 30.
 19Sn-NMR PARAMETERS 145

Comparison of the 3J(119Sn13C)values in trimethyl(1-propeny1)stannane

and 1,1,4,4-tetramethyl-l-stanna-2,5-cyclohexadiene shows that the two
equivalent coupling pathways contribute roughly additively to 3J(Sn13C) in
the latter compound.

Me,Sn
r7LICH3 Me2Sn mI3CMe,
\=/
)J( 19Sn13C)ci,(Hz): 49.390 88.0242

A considerable number of 35(119Sn13C)values are available in which

the 13C atom is part of an aromatic or heteroaromatic system. In general,
a range of -30-60 Hz is observed and in most cases it is found that
I35( 9Sn13C)I > IzJ( 9Sn13C)I. !2 5
In allenyltrimethylstannanes,3J(119Sn13C)is found to range between 45
and 70 Hz. No obvious dependence on the nature of the substituents has been
derived so far.1s4*247*248
There are plenty of examples of 3J(119Sn13C) with one or two atoms, other
than carbon, in between the coupled nuclei. In most cases, no systematic study
has been carried out. However, the potential of this parameter has been shown
in a study of B- and N-(trimethylstanny1)aminoboranes. Particularly
noteworthy are the two following isomeric compounds for which a barrier to
rotation about the B-N bond is shown by the differing couplings":
13J(119Sn13C)ltrans> 13J(119Sn13C)l,i,.

Me&\ ,CH, CH3, ,SnMe,

B-N
\ ,B-N \
Me,Sn/ CH, CH, SnMe,

trans 88.4 48.4

cis 78.9 33.0

The greater value of 135(119Sn13C)Iis associated with the coupling path

19Sn-B-N-13C. This is qualitatively in agreement with predictions that
assume dominance of the contact term. The strongly polarized Sn-N bond
(coupling pathway l19Sn-N-B-13C) reduces the 19Sn s electron participa-
tion as compared with the much less polar Sn-B bond.
Many organotin compounds of the type (R,Sn),X or (R,SnX), (X = N, P,
0, S, Se, Te) have been studied by 13C NMR.76*143 In all cases studied the
35(119S XSn13C) couplings are small (c12 Hz), and frequently they are not
observed at all. The same behaviour is found for the coupling pathways
119Sn-C-Sn-'3C,243 "9Sn-Sn-Sn-'3C,'67 or 119Sn-Si-Sn-13C.76 This is
 146 BERND WRACKMEYER

also observed to a lesser extent for the introduction of X = N, 0, S instead of

carbon atom^.^^^*^^^*^^^
c. 3J( '19Sn119Sn). The rapid development of organotin chemistry has
led to numerous compounds containing two or more tin atoms separated by
three bonds with various intervening atoms. Changes in t3J(119Sn"9Sn)l are
expected to correspond to those observed for I3J(' 19Sn13C)Iand, therefore,
indirect structural information will become available. So far a fairly complete
data set is available for 19Sn' 19Sn)couplings across C=C double bonds
in methyltin derivatives. This shows that I3J(l 19Sn119Sn)(trans
> 13J(119Sn119Sn)Jcis, although the value of 13J(1'9Sn1'9Sn)l in 1,Cdis-
tannacyclohexadiene is much larger than predicted from the additivity of the
two equivalent coupling pathways:

H\ /H
H,
,c=c
,SnMe3
Me,Sn
nSnMe,
Me,Sn
,c=c \
SnMe, Me3Sn \H L 7 . l

,J( I9Sn1I9Sn) (Hz): 491251 1013251 162OZ4'

If the intervening carbon atoms are sp3 hybridized the values of

I3J(l 19Sn"9Sn)l become smaller when electropositive substituents are at-
tached to the carbon atoms:
Me,Si, Me,Sn
\
Me,SnCH,CH,SnMe, CH-CH,-SnMe, CH-CH,-SnMe,
/ /
Me& Me3%
3J ( 1 1 9 SnlL9Sn)(Hz): 1101251 458'' I 61 1'"

The increase in I ,J(' "Sn"'Sn)l in the 1,1,2-tris(trimethylstannyl)ethane

as compared to the 1,2-bis(trimethylstannyl)-1-trimethylsilylethane can be
traced to its dependence on dihedral angle. In the former compound there are,
on average, more positions with a small or large dihedral angle between the
relevant Sn-C bonds than in the latter compound.
The values of ,J(' '9Sn' 9Sn)in bis(trialky1stannyl)ethynes are fairly small
and solvent dependent.' 5 9 Interestingly, no Sn-Sn coupling is observed in the
dicobalthexacarbonyl complexes of these ethynes. It is assumed that the
Sn-C-C bond angles (> 135") in the complexes lead to weak electron
correlation between the two Sn-C bonds.252
The temperature dependence of ,J( 19Sn119Sn)in 1,2-dimethyl-l,2-
bis(trimethylstanny1)hydrazine (from 272 to 222 Hz between - 30 and
+ 1 OOOC) has been attributed to changing populations of conformations with
anti and gauche arrangement of the Me,Sn groups."'
The finding of a very large value of J3J(1'9Sn119Sn)l(25,430 Hz) across a
Pt-Pt bond in [Pt2(SnCI,)2(p-dppm)2]225 (dppm = Ph,PCH,PPh,) fits into
the somewhat abnormal behaviour of "J(l I9SnX) data in SnCl, complexes.
 'Sn-NMR PARAMETERS 147

TABLE 19
Tin nitrogen and organotin nitrogen compounds,' tin coordination number 2

Compound 6'"Sn Solvent Footnotes Reference

Me,SnNMe, + 75.5 10% C6H6 b 320

Me,SnNEt, +60 25% C6H6 b 320
Me,SnN(H)Ph + 46.4 C6H6 12
Me,SnN( Me)Ph + 73.0 C6H6 118

Me,Sn-N
3
Me,SnN(Bu')SiMe,
+ 72.9
+ 30.8
C6D6

20%C6D6
76

212
MeSnN(Ph)SiMe, +64 50% C6H6 9
(Me,Sn),NMe +81.0 20%C6D6 212
(Me,Sn),NBu' +40.7 20% C6D6 212
(Me,Sn),NPh + 63.0 20% C6D6 212
(Me,Sn),NC,H,-p-Me + 62.7 20%C6D6 212
(Me,Sn),N-C,H,-o-Me + 64.0 20%C6D6 212
Me,SnN(SiMe,), + 46.7 20% C6D6 212
(Me,Sn),NSiMe, + 66.0 20% C6D6 212
(Me,Sn),NSiMe,Cl + 70.8 20% C6D6 212
(Me,Sn),NSiMeCI, +79.1 20% C6D6 212
(Me,Sn),NSiCI, + 87.0 20% CdD6 212
Me,SnN(GeMe,), +61.4 20%C6D6 212
(Me,Sn),NGeMe, + 73.3 20% C6D6 212
(Me,Sn),N + 86.3 20% C6D6 212
Me,SnN(Bu')PbMe, +47.0 20% C6D6 212
(Me,Sn),NPbMe, + 94.3 20% C6D6 212
Me,SnN(PbMe,), + 103.3 20% C6D6 212
(Me,Sn),NBMe, + 47.5 20% C6D6 212
+45.0 Toluene 18

(Me,Sn),NB
3 Me
Me
+47.0 20% C6D6 212

I
(Me,Sn),N-B
"3
\N
I
+61.7 20% CsD6 212

Me
Me
/Me
,B,N
Me,SnN 1 +45.3 C6D6 18
\ B ~ ~
Me 'Me
Me ,Me
,N,B
Me,Sn-N I + 44.0 C6D6 18
\
B"
Me 'Me
 148 BERND WRACKMEYER

T A B L E 19 (cont.)
Compound 6119Sn Solvent Footnotes Reference
Me,SnNH-NHPh + 59.5 C6D6 76
Me,SnNMe-NMeSnMe,
(a) (b)
+49.0 Toluene-d, 100
Me,SnNH-NPhSnMe, + 64.9 (a) C6D6 76
+49.5 (b)
(Me,Sn),N-NMe, + 49.0 Toluene-d, 100
(Me,Sn),N-NHPh +81.0 C6D6 76
(a) (b)
(Me,Sn),N-N(Me)SnMe, +61.5 (a) Toluene-d, 100
+ 56.7 (b)
(Me,Sn),N-N(Ph)SnMe, + 79.5 (a) Toluene-d, 100

’
+49.8 (b)
(Me,Sn),N-N(SnMe,), + 65.3 Toluene-d, 100

C0,Me
,&
1 CO,Me
+ 107.1
Me,Sn-N
’\ A SiMe, 32 1

C0,Me
C0,Me
Me,Sn-N, , + 101.7 32 I
hMe,
Me,%-NCO + 82.7 20% C6H6 b 322
Me,Sn-NCS + 58.7 20% C6H6 b 322
Bu,SnNEt, + 36.4 - 2
Me,Sn(NMe,), + 58.8 25% c6H6 320
Me,Sn(NEt,), +45 50% C6H6 b 320
Me,Sn[N(CH,)Ph], + 30.5 C6H6 118

+ 15.2 CDCI, 16

(Me,SnNMe), + 92. I Saturated C6H6 4

(Me,SnNEt), + 76 90% C6H6 4
SiMe,
I
Me,Sn/N] + 104.2 C6D6 76
‘N
I
SiMe,
Bu‘
I
N
Me,Sn’ ‘SnMe, + 108.9 C6D6 323
N
‘’
I
Bu’
 ''9Sn-NMR PARAMETERS 149

T A B L E 19 (cont.)
Compound 61I9Sn Solvent Footnotes Reference

But
I
N
Me,Sn< >Me +111.0 C6D6 323
N
I
Bu'
Me,Sn~(Me)C(O)CH,],NMe -63.3 CDCI, 63
Me,Sn(NCS),(dipy), - 363 20% D M F C 57
Me2Sn(NCS),(2,2',2"-tripyridyl) -409 20% D M F 57
Et,Sn(NMe,), - 67 20% CCI, 277
Et,Sn(NEt,), +21 - 277
Et,Sn[N(Me)C(O)CH,],NMe - 109.2 CDCI, 63
Bu",Sn(NEt,), - 18 - 2
Bu',Snm(Me)C(O)CH,],NMe -200.7 CDCI, 63
MeSn(NMe,), -15.1 25% C6H6 320
MeSn(NEt,), -24 25% C6H6 320
MeSn [N(Me)Ph] , -66.0 C6H6 118
BuSn(NEt,), -44 - b 2
Me,Sn(NEt,)CI +75 30% C6H6 d 4

+44.9 CDCI, 76

88.3 (a) TOlUene/C6D,j 314

100.7 (b)
88 (a) C6H6
8
100(b)

+115.7(a) 314
+ 109.3 (b)
+ 114 (a) C6H6 8
+ 109 (b)

- 156 C6H6 8
- 121.8 CH,CI, 279
- 121.6 - 2
- 122 - 2
- 175.6 C6H6 118
+ 120 Pentane 324
+767 ? e 75
+ 776 C&/C,D,, 80°C 366

For more 6'I9Sn of tin nitrogen compounds see reviews 3 and 4; for 'J(''9Sn1SN) data see Table 29.
For other conditions see review 4.
dipy, 2,2'-DipyridyL
lI9Sn resonance is shifted to higher frequency on dilution.
'6'19Sngiven as +720 relative to (Me3Si),NSnMe3.75
 150 BERND WRACKMEYER

TABLE 20
Tin-phosphorus, tin-arsenic, tin-antimony, and tin-bismuth bonded compounds, tin coordination
number = 3 or 3 4

Compound 6119Sn" Solvent Footnotes Reference

Me,SnPEt, - 11.1 (665.3) C6D6 325

Me,SnPBu', - 37.8 (792) C6D6 326
Me,SnPHPh + 18 (+ 538) 10% C6H6 199
9
Me,SnPPh, - 3.0 ( + 586) 50% C6H6 b 199
9
- 2.3 ( +596) 65% C6H6 175
(Me,Sn),PEt + 25.7 (nr) C6H6 C 325
(Me&), PBu' -0.1 (816) C6D6 326
(Me, Sn), PPh + 14.2 ( +724) 90% CH,CI, 175
(Me,Sn),P + 36.3 ( +832.5) 65% C6H6 175
+ 37.2 (829) C6D6 d 212
+ 38.0 (834) C6D6 326
+ 37.8 (833.7) C6D6 325
[Me,SnPBu',-Mn(NO),] + 1.2 (137) C6D6 326
[Me3SnPBu',-Fe(C0)(N0),1 -4.5 (106.6) C6D6 326
[Me,SnPBu',-Co(CO),NO] - 10.3 (107) C6D6/THF 326
[Me,SnPBu',-Ni(CO),] - 20.7 (149) C6D6 326
[Me,SnPPh,-W(CO),] + 33.7 ( +50) C6H6 175
[(Me, Sn), PBu'-Mn(NO),] + 29.3 (286) C6D6 326
[(Me, Sn), PBu'-Fe(CO)(NO),] -23.4 (264.5) C6D6 326
[( Me,Sn),PBu'-Co(CO),NO] + 18.1 (268) C6D6/THF 326
[( Me,Sn),PBuL-Ni(CO),] + 9.3 (304) C6D6 326
[(Me,Sn),PPh-Cr(CO),] + 39.7 ( + 253) C6H6 175
[(Me,Sn),PPh-W(CO),] +41.6 (+216) C6H6 175
[(Me, Sn), P-Cr(CO), 1 +64.2 (+409.5) C6H6 175
[(Me3 Sn)3p-w(Co), 1 + 63.4 (+ 375.5) C6H6 175
[(Me, Sn), P-Mn(NO), 1 + 62.0 (399) C,D,/CDCI, 326
C(Me3Sn)3P-Fe(CO)(NO)zl + 56.9 (385.7) C6D6 326
[(Me,Sn),P-Co(CO),NO] + 50.6 (393) C6D6/THF 326
[(Me&), P-Ni(CO),] +44.9 (429) C6D6 326
(Me&), AsPh - 1.7 C6H6 212
(Me,Sn),As + 6.0 C6D6 327
(Me,Sn),Sb -90.0 C6D6 327
(Me,Sn),Bi - 110.0 C6D6 327
[(Ph, Sn), PI - -4.6 (1476) THF/C6D6 328
Me, Sn(PPh,), - 11.5 (+808) C6D6 118
[Sn(PBu',),l, + 328 (1800,t) 92, 318
(1086,d)
SnC1,-PEt, - 47.3 Toluene, C6D6 e 56
SnCl,-PBu', -48 Toluene, C6D6 e 56
SnCI,-PBu', +21 Toluene, C6D6 e 56
SnCI,-P(NMe,), - 195 e 329
 lI9Sn-NMR PARAMETERS 151

TABLE 20 (conr.)
Compound 6''9Sna Solvent Footnotes Reference
SnCI,( PBu",), - 573 (2395) CHZCI,, -30°C 64
SnCI,Br( PBu",), -658 (2280) CHZCI,, -30°C 64
SnCI,Br,( PBu",),
trans -738 (2175) CHZCI,, - 30°C 64
cis -750 (2170) CHZCI,, -30°C 64
SnCIBr,( PBu",), - 837 (2065) CHZCI,, -30°C 64
SnBr,( PBu",), -935 (1960) CHZCI,, -30°C 64
[SnCI,-PBu",]- -652 (2020) CHZCI,, -30°C 64
[SnCI,Br-PBu",]-
P,CI-trans -783 (1865) CHZCI,, - 30°C 64
P,Br-trans - 837 (2010) CHZCI,, -30°C 64
[SnCI,Br,-PBu",]-
P,Cl-trans, -913 (1720) CH,CI,, - 30°C 64
Cl,Cl-trans
P,Cl-trans, -927 (1710) CHZCI,, -30°C 64
CI,Cl-cis
[SnCI, Br,-PBu",] -
(P,Br-trans) -986 (1865) CHZCI,, -30°C 64
[SnCI,Br,-PBu",]-
(P,Cl-trans) - 1069 (1565) CHZCI,, -30°C 64
[SnCI,Br,-PBu",]-
P,Br-trans, - 1132 (1720) CHZCI,, -30°C 64
Br,Br-trans
P,Br-trans, - 1144 (1720) CHZCI,, -30°C 64
Br,Br-cis
[SnCI,Br-PBu",]-
(P,Cl-trans) - 1225 (1405) CHZCI,, -30°C 64
(P,Br-trans) - 1301 (1555) CHZCI,, -30°C 64
[SnBr,-PBu",] - - 1470 (1415) CH,CI,, -30°C 64
Values 'J(119Sn3'P) are given in parentheses.
* For other conditions see review 3.
nr, Not reported.
Corrects a misprint (wrong sign) in reference 212.
Rapid exchange.

d. 3J( "Sn " B ) . Owing to the rapid quadrupolar relaxation of the "B
nucleus the scalar coupling 3J(119Sn11B)is partially relaxed in most cases.
However, when the molecule is sufficientlysmall or when the symmetry at the
B nucleus is approximately tetrahedral the coupling may just be resolved 36
if 3J(119Sn"B). T,("B). 27c > 1.
In the case of efficient scalar relaxation of the second kind, the lI9Sn-NMR
spectra still yield information on the stereo~hemistry.~' This is readily shown
in Fig. 9, in which two broad II9Sn resonances are observed. The broader
152 BERND WRACKMEYER

FIG. 9. 'I9Sn{ 'H}-NMR spectrum at 74.63 MHz of 1,1-bis(trimethylstanny1)-2-

diethylboryl-I-butenein hexane/C,D,, 28°C.

signal can be assigned to the tin atom in the position trans to the ''B nucleus,
'
assuming that I J(' "Sn' B) ' '
> I J(' 9Sn1 B) leis.
Therefore, in addition to the d119Sn values, the linewidths of the '"Sn
resonances, in appropriate compounds, may serve as structural tools.
e. Other vicinal couplings, 'J(SnX). Some values of I3J(' "SnX)I across
the C=C triple bond in alkynylstannanes have been reported (X = "Si,
'07Pb, lgsPt). These values are small in the case of X = zgSi's7 or z07Pb'59
and fairly large for X = 195Pt.253
The I3J(1rgSn'gF)I couplings are large in perfluoroethyltin compounds
(220-275 Hz)'" and small in perfluorovinyltin compounds, 25 (cis) and 29
Hz (trans).236No systematic study has been carried out so far.'84

4. "J(SnX) couplings (n 2 4 )
In many cases it is possible to observe long-range couplins, "J("9SnX)
(n 2 4). However, the data set available is insufficient for most X nuclei to
reach firm conclusions regarding the structure and the bonding situation.
Corresponding long-range couplings, "J(' 3C'H), "J(I3C' 3C), "J ( "Si'H),
etc., have deserved only scant attention so far and in most cases analogous
organotin compounds are not available or they have not been studied in
detail by NMR. It is certain that developments in NMR instrumentation
will facilitate the access to long-range couplings in general. In the case
of organotin compounds, with the possible exception of allenyl
~ t a n n a n e s , ~discussion
~ ' * ~ ~ ~ of the data should be postponed until more
material is available for comparison.
 "Sn-NMR PARAMETERS 153

TABLE 21
Tin-silicon, tin-germanium, tin-tin, a d tin-lead bonded compounds, tin coordination number 9 4
Compound 6119Sn" Solvent Footnotes Reference

- 126.7 90% C6H6 12

+
( 656) 319
(580)
Me,Sn-SiPh, - 149 CDCl,/dioxane 330
(Me,Sn),Si - 34.0 C6D6 212
(220)
(Me,Sn),SiLi - 1.0 C6D6/THF b 212
(no)
[SnGe,14- - 1233 en 82
[Sn,-,Ge,] (n = 1-7) - 1230 to en 82
-1180
Me,Sn-SnMe, -113 90% C6H6 8,205
(4460)
- 109 - b 278
(no)
- 108.7 95% C6D6 331,167
(4404)
- 109.0 C6D6 b 255
(no)
- 109.2 MeOH b 332
(no)
(a) (b)
Me&-Sn(Et)Me, - 107.8 (a), b 255
-92.1 (b)
(no)
(a) (b)
MeSn-Sn(chex)Me, - 107.9 (a), b 280
-95.7 (b)
(no)
(a) (b)
Me&-SnEt, - 109.0 (a), C6D6 b 255
-62.6 (b)
(no)
- 108.1 (a), 95% C6D6 331
-61.8 (b) 167
(3496)
- 108.9 (a), 95% C6D6 167
- 88.8 (b)
(3551)
- 105.4 (a), 95% C6D6 167
- 32.4 (b)
(2832)
- 108.6 (a), 95% C6D6 167
- 82.1 (b)
(3505)
 154 BERND WRACKMEYER

T A B L E 21 (cont.)
Compound 6"9Sna Solvent Footnotes Reference
(a) (b)
Me,Sn-SnBu", - 105.3 (a), 331, 167
-45.3 (b)
(2810)
(a) (b)
Me,Sn-Snchex, - 103.8 (a), 33 1
- 78.3 (b),
(2841)
(a) (b)
Me,Sn-SnPh, -91.5 (a), 12
- I53 (b)
(4240)
-91.5 (a), 331, 167
- 150.6 (b)
(4262)
(a) (b)
(Me,Sn),SnMe, -99.5 (a), 167
-261.7 (b)
(2873)
- 100.8 (a), 166
- 263 (b)
(2900)
(a) (b)
(Me,Sn),SnEt, -99.1 (a), 167
- 199.1 (b) 255
(2375)
(a) (b)
(Me,Sn),SnPr', - 97.0 (a), 167
- 139.5 (b)
(1957)
(a) (b)
(Me,Sn),SnMe - 89.5 (a), 333
-489.7 (b)
(1 733)
(a) (b)
(Me,Sn),SnEt - 89.3 (a), 333
-440.9 (b)
(1538)
(a) (b)
(Me,Sn),SnBu" - 90.3 (a), 333
-459.9 (b)
( I 548)
(a) (b)
(Me,Sn),SnBu' -90.8 (a), 333
- 480.4 (b)
(1 546)
(a) (b)
(Me,Sn),SnC,H, ," - 90.1 (a), 333
+460.5 (b)
(1 535)
- 83.2 (a), 333
-434.2 (b)
(1670)
 '''Sn-NMR PARAMETERS 155

TABLE 2l(cont.)
Compound 6''9Sn" Solvent Footnotes Reference

- 80 (a), C6H6 b 3
-806 (b)
(no)
- 80 (a), C6D6 212
- 739 (b)

(881)
-96.8 (a), C6D6 b 255
-248.6 (b)
(no)
Me,(Ph)SnSn(Ph)Me, - 120.2 C6D6 334
(4153)
Et ,Sn-SnEt , - 59.9 95% C6D6 33 1
(2702) 167
(a) (b)
Et,Sn-SnBu", -65.7 (a), 95% C6D6 331
- 79.7 (b) 167
(2688)
-48.7 (a), 95% CdD6 331
- 140.4 (b) 167
(3153)
- 56.0 (a), 95% C6D6 167
- 272.8 (b)
(1931)
- 54.8 (a), 95% C6D6 167
-205.9 (b)
(1481)
- 57.3 (a), 95% C6D6 167
- 139.3 (b)
(1153)
- 63.9 (a), 95% C6D6 b 167
-214.4 (b)
(no)
-29.1 95% C6D6 331
(1208) '167
-31.2 ? 280
(1216)
(a) (b)
Pr',Sn-Sn(chex)Pr', -31.9 (a), ? 280
-43.9 (b)
( 1226)
(a) (b)
(Pr',Sn),SnMe, - 34.3 (a), 95% C6D6 167
-272.1 (b)
( 1366)
 156 BERND WRACKMEYER

T A B L E 21 (cont.)
Compound 61'9Sn" Solvent Footnotes Reference

-31.0 (a), 95% C6D6 b 167

- 206.7 (b)
(no)
- 35.0 (a), 95% C6D6 167
- 132.9 (b)
(403)
Pr ',(Bu')SnSn(Bu')Pr', -21.5 95% C6D6 331
(764) 167
Pr ',(chex)SnSn(chex) Pr ', -44.4 ? 280
(1237)
(a) (b)
Pr',(chex)SnSn( Pr')chex, -45.6 (a), ? b 280
- 58.2 (b)
(no)
chex,( Pr')SnSn( Pr')chex, - 57.8 ? b 280
(no)
Bu",Sn-SnBu", - 79.5 - b 278
(no)
- 83.2 95% C6D6 331
(2748) 167
(a) (b)
Bu',Sn-Snchex, - 93.2 (a), 95% C6D6 167
- 85.2 (b)
(2533)
- 86.8 (a), CDCI, 33 1
- 146.9 (b) 167
(3199)
(a) (b)
(Bu',Sn),SnBu', -92.8 (a), 95% C6D6 167
- 236.2 (b)
(1590)
Bu',SnSnBu', - 3.4 CDCI, 167
(<W
-64.7 (a), CDCI, 167
- 134.1 (b)
(2260)
(a) (b)
(chex,Sn),SnBu', - 84.3 (a), 95% C6D6 b 167
-224.8 (b)
(no)
oct",SnSnoct", - 83.5 95% C6D6 167
(2705)
Ph,SnSnPh, - 143.6 CDCI, 167
(4470)
- 144.2 C6D6 b 285
(no)
 "Sn-NMR PARAMETERS 157

TABLE 2l(cont.)
Compound '
6' 9Sna Solvent Footnotes Reference
~

(a) (b)
(Ph,Sn),SnBu', - 138.2, CDCI, 167
-221.0
(2273)

,
Me,Sn-SnMe,
/ \
H(Me)C /C(Me)H -67.1 C6D6 25 1
(3567)
Me,Sn-SnMe,
Me&-SnMe,
/ \
\
Me@-SnMe,
FMe2 -53.1
(2878)
C6D6 25 1

Ph,Sn-SnPh,
/ \
HZC\ CHI - 109.3 CDCl, 335
/ (4159)
Ph,Sn-SnPh,
[(2*6-EtZ-C6H3)ZSn13 C6D6 b 312

Me,Sn-SnMe,
x/\x
'Sn'
Me,
x=s +44 (Sn,) C6H6 16
(39771,
+
176 (Sn)
X = Se +21 (Sn,) C6H6 168
(3466),
+
82 (Sn)
X = Te -38 (Sn,) C6H6 168
(2643)-
-164(Sn)
Me,(Cl)SnSn(CI)Me, + 19.0 MeOH 332
(no)
Me
C
'0 '
0
I I
Bu",Sn-SnBu", - 126.8 CDCl, 167
I I (11,272)
O, /O
C
Me
 158 BERND WRACKMEYER

T A B L E 2l(cont.)
Compound bLL9Sna Solvent Footnotes Reference

- 208 CDCI,, 31°C 336

(1117)

I
C
'0 '
0
I I
Me,Sn-SnMe,
I I

R
R
-
H - 135 C6D6 b 337
(no)
- 122 CDCI, 337
(13,056)
Me - 128 CSDS 337
(14,980)
-117 CDCI, 337
(14,549)
CHZCI -95 C6D6 b 337
(no)
- 86 CDCI, b 337
(no)
CHCI, - 57 C6D6 337
(12,622)
CCI, - 15 C6D6 337
(12,323)
CF, -44 C6D6 337
(1 1,424)
NMe,
I

337

I
NMe,
 "'Sn-NMR PARAMETERS 159

TABLE 21 (cont.)
Compound 6119Sna Solvent Footnotes Reference

P
s' s'
I 1
Me,Sn-SnMe, - 22 C6D6 337
II I (1 2,119)

P
2

CSn412- - 1895 en 82
(1281)
- 1230 en d 80
(266) 81
- 1230 en e 338
(no) b
[Sn,TI15- -1167 en, 30°C 82
(429, Sn)
(800, n)
Me,Sn-PbMe, - 57.0 C6H6 13
(- 3570)
Ph,Sn-PbMe, - 119.5 C6H6 13
(- 2800)
[Sn,-,Pb,]'- - 1270 to en f 80,81
- 1600
(270, Sn)
(560, Pb)

Values of 1J(119Sn29Si),1J(119Sn119Sn), O ~ ' J ( ~ ~ ' P ~(Hz)

" ~ Sin ~parentheses.
)
no, Not observed or not reported (?).
Assignment of 1J(119Sn11gSn)uncertain since 1J(119Sn125Te)(2554 Hz) is in the same order of
magnitude.
dNonrigid structure; the same l19Sn-NMR spectrum was obtained at -40°C in liquid NH,.
' Broad signal; the large line width (1 100 Hz) is attributed to the presence of paramagnetic [Sn,]'-.
'The shielding of the Il9Sn nuclei is increased fairly regularly by 42-60 ppm with increasing n.

VI. CONCLUSIONS

Many recent achievements in tin chemistry are based, at least partly, on

"'Sn-NMR parameters and there can be no doubt that this is a flourishing
area. This is also evident from the steadily increasing number of references
cited for the years 1978-1983. Although we are still far from understanding all
of the trends in 'I9Sn chemical shifts or couplings involving the "'Sn
nucleus, even in a qualitative sense, our general position has improved
 160 BERND WRACKMEYER

TABLE 22
Ti-Group I11 element bonded compounds,* tin coordination number 3 4

Compound 6119Sn0 Solvent Footnotes Reference

[Me,SnBH,]- - 28.5 (- 554) THF/C6D6 b 18

Me3SnB(C1)NMe, - 139 (- 1007) - 12,14
Me,SnB(OMe)NMe, - 161.5 (-947) C6H6 14
Me,SnB(SMe)NMe, -127(-717) C6H6 14
Me,SnB(NMe,), -150(-953) C6H6 12, 14, 18
Me
I

Me,Sn{] N 152.3 (-930) C@6 13,14, 18

I
Me
(Me,Sn),BNMe, - 149 ( -657) Toluene 14,18
Me,Sn(Me,N)BB(NMe,)SnMe, - 150 (-865) Toluene 18
[Me3SnTlMe3] - - 376.5 (nr) Dimethoxyethane C 4
[Sn,TI]'- - 1167 (429,Sn) en d 82
(800,W
* Broad singlets at low frequency are reported for 1-Sn-2-[SiMe3]-R-2,3-C2B4H4(R
= H, Me, SiMe3).368
Values of 1J(119Sn11B)and 1J(119Sn20STl)(Hz) are given in parentheses.
* 6"'Sn and 1J(119Sn11B)change slightly with concentration and solvent.
nr, Not reported; 1J(205T1119Sn)= 11,610Hz is given for [(Me,Sn),Tl- in reference 4.
Non-rigid structure; values of 1J(119Sn119Sn)and 1J(205T1119Sn)(Hz) are temperature dependent;
en (30to 1 lo")429-425 Hz and 793-842 Hz, respectively; liquid NH, (- 74 to - 34°C)457-419 Hz and
927-1001 Hz, respectively.

considerably: (1) With modem equipment there are, in principle, no serious

experimental difficulties in observing 19Sn resonances either directly or by
heteronuclear double resonance; (2) our knowledge of the 19Sn relaxation
behaviour is increasing ,which allows for the proper choice of experimental
conditions to observe the l19Sn resonance (in addition to the elucidation of
other features connected particularly with the relaxation mechanism);
(3) d119Sn data, which become increasingly available for all kinds of tin
compounds, help one to use this parameter in an empirical way and to find
models for the qualitative interpretation of d119Sn; (4) this also applies to
couplings involving the l19Sn nucleus, which have already been shown to
serve as a sensitive tool in the discussion of structure and bonding.
All this concerns measurements in the liquid state. There are, of course,
many applications of 19Sn-NMR parameters of tin compounds, partially
oriented in liquid crystal solvents. For various reasons these results have not
been included here. Considering the enormous potential of solid-state NMR
 ' '9Sn-NMR PARAMETERS 161

TABLE 23
Tin-lithium compounds

Compound 6Il9Sn Solvent Footnotes Reference

- 183 20% TH F 9
- 180.7 20% T H F 339
- 179 THF 280
- 182.7 THF a 340
-99 THF a 340
- 130 THF 280
- 13.0 TH F 280
- 109 THF(?) 280
-123(a), -194(b) TH F h 280
-48.2 (a). THF h 280
- 39.3 (b)
- 104.6 to - 107.1 (a) TH F C I56
- 1031.2 10 - 1042.1 (b)
- 5200 to
-4445 ['J(SnSn)]
- 101.7 (a) THF, C,D, 212
- 1044 ( - 5737) (b)

Mixtures of R,SnSnR, and R,SnLi (R = Me, Et) have been studied by Il9Sn NMR.340
* Assignment of Sn(a, b) needs confirmation.
' Values of 6' "Sn and 'J(SnSn) (Hz)differ for two samples of different age and concentration.

and the steadily growing number of commercial instruments capable, e.g., of

'
magic-angle sample spinning (MASS), high-power H decoupling, and cross
polarization (CP), it is easy to predict forthcoming applications of '19Sn
solid-state NMR. In addition to the interesting practical aspects we may learn
more about '19Sn nuclear shielding from the tensorial components of the
averaged isotropic shielding.

ACKNOWLEDGMENTS

I thank the Deutsche Forschungsgemeinschaftand the Fonds der Chemischen

Industrie for generous support of my experimental and spectroscopic studies.
I am indebted to Prof. Noth for his stimulating collaboration, and to my
research students for their excellent experimental work. It is a pleasure to
thank my wife for her patience and her careful work in typing the manuscript.
 U
W
A
i'
l l l l l ~ l l l Il I I I I I I I I I I I I I I I
2
162
 + 2.9 1470 1560(’J) C6D6 56,362
-2.6 1440 - C6D6 56
-217.6 1610 C6D6/THF 56
- 198 - C6D6/THF 56
+ 63 C6H6 260
+ 66.3 C6H12 278
+ 150 C6H6 260
+ 284 CDCl, 260
- 89 C6D6 260
-223 CDCl, 260
+ 79 C6H6 260
+257 C6H6 260
+ 147 C6H6 260
+ 58.2 C6D6 285
-401 (FeSn), C6H6 166
- 103 (SnSn)
+ 151 C6H6 260
+ 293 C6H6 260
+483 C6H6 260
+ 172 CHZCI2 b 260
- 106 CH2C12 b 260
- 123 CH,C12 b 260
+ 79.3 Toluene/C6D6 316
+ 35.3, Toluene/C6D6 C 316
+
24.0
- 159,
-249.8
cispans-[PtH(Me)(SnPh,),(bipy)] -74.2 6641 CHzC12 d 200
cis-[ Pt(SnMe,)(C=CPh)(PPh,),] -46 - CHzCl2 260
1587 (trans) CHZCl,
104 (cis)
 TABLE 24(cont.)
'J(M119Sn) 2J(1'9Sn31P)
Compound 61'9Sn (H4 (H4 Solvent Footnotes Reference

Me),]
cis-[Pt(SnMe3)(C~CPh)(PPhz -48 - - Toluene-d8 260
cis-[ Pt(SnMe,)(CF=CF,)( PPh,),] 0 - - CDCl, 260
cis-[Pt (Sn(CH,),}(Ph)(PPh,),] -0.3 - 1673 (trans) C6H6/C6D6 341
161 (cis)
cis-[Pt(SnPh,)(Ph)( PPh,),] - 106 12,686 1934 (trans) CH,Cl, 190
161 (cis)
cis-Pt(SnPh,CI)(Ph)(PPh,),] + 32 14,066 2398 (trans) CH,CL, 190
151(cis)
cis-[Pt(SnPhCI,)( PhWPPh,),] + 56 16,889 2959 (trans) CH,CI, 190
195 (cis)
cis-[Pt(SnPh,Br)( Ph)(PPh,),] +29 13,940 2398 (trans) CH,Cl, 190
5 cis-[Pt(SnPh~r,)(Ph)(PPh,),] +47 16,241
152 (cis)
2954 (trans) CHZCI, 190
183 (cis)
cis-[Pt(SnPh,I)(Ph)(PPh,),] +2 13,735 2380 (trans) CHzCl, 190
153 (cis)
cis-[Pt(SnPh, SCH, Ph)(Ph)(PPh,),] -7 13,416 2167 (trans) CH,CI, 190
159 (cis)
cis-[Pt(SnPh,SPh)(Ph)(PPh,),] -4 13,306 2185 (trans) CH,CI, 190
153 (cis)
cis-[Pt(SnPh,NCS)( Ph)(PPh,),] - 17 14,050 2375 (trans) CH,Cl, 190
159 (cis)
cis-[PtCI(SnMe,CI)(PPh,),] + 196 8,921 2267 (trans) CHzCl, 190
65 (cis)
cis-[PtCI(SnBu",Cl)(PPh,),] +116 8,821 204 (trans) CHzCl, 190
43 (cis)
cis-[PtCI(SnBu',CI)(PPh,),] +81 8,800 1853 (trans) CHZCI, 190
21 (cis)
 ci~-[PtCl(SnMeC1,)(PPh~)~] + 77 13,105 3119 (trans) CHZCI, 190
128 (cis)
cis-[ PtCl(SnBu"Cl,)(PPh,),] + 67 12,320 2911(trans) CH,CI, 190
105 (cis)
cis-[PtCI(SnPhClZ)(PPh3),] -31 13,940 3223 (trans) CH,Cl, 190
122 (cis)
cis-[PtBr(SnMe~Br)(PPh,),l +98 8,928 2264 (trans) CHZCIZ 190
49 (cis)
cis-[ PtBr(SnBu",Br)(PPh,),] +113 8,191 2039 (trans) CHZCIZ 190
24 (cis)
cis-[PtBr(SnMeBr,)(PPh,),] +38 11,896 3082 (trans) CHzC12 190
104 (cis)
cis-[ PtBr(SnBu"Br,)( PPh,),] +44 11,156 2881 (trans) CHIC12 190
80 (cis)
cis-[ PtBr(SnPhBr,)( PPh,),] +32 12,361 3195 (trans) CHzC12 190
101(cis)
e
trans-[PtCl (SnMe,Cl)(PPh,),] + 120 14,788 131 CHZCI, 190
trans-[PtCl(SnBu",Cl)(PPh,),] +81 13,294 119 CHZCIZ 190
trans-[PtCl(SnMeCI,)(PPh,),] - 18 19,982 165 CH,Cl, 190
tr~ns-[PtCI(SnBuCl~)(PPh,)~] -2 18,534 155 CHIC12 190
tram-[PtC1(SnPhCl2)( PPh,),] +60 8,020 244 CHZCIZ 190
trans-[ PtBr(SnMe, Br)(PPh,),] + 29 14,654 128 CHZCIZ 190
trms-[PtBr(SnBu",Br)(PPh,),] + 78 13,062 116 CHZCI, 190
truns-[PtBr(SnMeBr,)(PPh,),] -63 18,361 153 CHZCl, 190
tram-[ PtBr(SnBu"Br,)(PPh,),] + 26 17,877 140 CH,CI, 190
tr0ns-C PtBr(SnPhBr,)( PPh,),] -57 7,880 223 CH,Cl, 190

a Other signals: 6119Sn+61.5, +44.4, and more.

* Undefined stereochemistry
Undefined structure.
'bipy, Bipyridyl.
 TABLE 25
Transition metal tin halides, tin coordination number 2 4

'J(M'I9Sn) zJ("9Sn"qSn) 2J("9SnJ'p)

Compound "'Sn (Hz) (Hz) (H4 Solvent Fwtnotes Reference

- 34.6 - 2474 (cis) 3 M HCI 222

13,460 (trans)
- 167.9 (q) 846 (4 3075 (cis. eq. eq) CH,NO, 227
- 149.2 (ax) 2701 (cis. eq.ax) 221
22,241( t r m , eq,eq)
[Ru(SnCI,),(MeCN)'- - 70.6 (eq) - 2760 (cis. eq. eq) CH,NO, 227
- 103.9 (UX) 2817 (cis, eq. ax)
18.296 (tram, eq. eq)
[Os(SnCI,),CI]' -531.8 (eq) 1290 ( 4 227qcis. eq, eq) CH,NO, 221
-581.8 (ax) 1614 (cis, eq. ax)
19,465 (from, eq. eq)
+ 8.5 806 3803 3 M HCI 219
- 100.5 547 2043 3 M HCI a 219
-204.3 590 2258 3 M HCI 219
-411.1 718 2934 3MHCI b 219
- 395.4 708 2972 12 M HCI 219
- 654.4 7% 3 M HCI 219
- 626 780 I2 M HCI 219
-991.6 864 3 M HCI 219
-914.1 850 I2 M HCI
+ 38.8 758 2523 CDCI, C 210
+ 25.7 651 1759 CDCI, d 210
+ so2 986 14.141 Acetone-d,. - 50-C 210
+89.1 864 9715 CDCI, 210
+ 156.7 845 CDCI, c 210
C66.6 757 1329 CDCI, C 229
C65.0 757 I700 Acetone. -M0C C 229
+71.8 757 1124 Acetone, - SOC' C 229
+ 66.8 157 932 Acetone. - 50-C C 229
+ 38.3 674 2875 Acetone, - 50'C d 229
+ 34.8 684 3538 Acetone. -50-C d 229
+44.1 67 I 2772 Acetone, - SOC' d 229
+39.1 671 3295 Acetone, - 50°C d 229
-268.7 - 1572 Acetone-d,. - 50'C C 210
-216.5 - 1583 CDCI, d 210
 3.SL -
161 - LLO‘~Z 661 -
“13’a3/zD‘H3
- S8S‘OZ 6P8 -
-
91s LES‘OE OLZ -
9L SWZ W‘LZ Ztl-
161 - E16‘91 ZEZ -
161 - SPL‘E 1 soz -
OIZ Em 8L9’PI B’PPI -
161 EOSZ 269‘ I Z OEPI -
OIZ P w m’rI S’ZEl-
OIZ J 6ZL ESSP’91 8’602 -
161 LS6’81 88L’61 6L -
161 8lE:Sl IE0‘61 L9 -
161 ILZL‘ I 6w.6 I LII-
161 E99‘81 ZZP‘OZ EL-
161 8E9‘8 I 6EZ‘OZ LL-
161 LZ0‘61 OIP‘OZ E8 -
I I2 ELW 566‘5 I Z’IZI -
9zz ‘LIZ OZS9 PZ0’9 I ZPI -
161 - - IEl-
161 - - OL-
161 - - Ell-
- -
161 SL-
161 Z86’8E - II+
161 - - 51 +
161 996’12 - El+
OIZ EPll - zEr +
8ZZ I ‘a - - OLI -
8ZZ Y‘J - - 9LI -
822 8‘a - - Z6l -
- -
822 /‘a L61-
622 P - - 9961 -
- -
6ZZ P P’861-
622 P - - P’80Z -
6ZZ P - - owz -
622 P SW - P’80Z -
622 P ZPEl - I’OIZ-
622 P 9161 - zon -
622 P 81PI - 9LIZ-
OIZ P ‘J
- - Z’99Z -
012 P - 6261-
OIZ 3 - 9 9 n-
 TABLE 25 (cont.)
IJ(M1IPSn) zJ("9Sn119Sn) 2J('19Sn3'p)
Compound "9Sn (Hz) (Hz) (Hz) Solvent Footnotes Refcrena

237

CH,CII. CD,CI,. 191

-75 c
- 250 27.222 - CDCI,, - ZS'C 191
- 59 16,321 4298 (trans) CDCI,, - 25OC 191
216 (cis)
- 72 16,931 4296 (trans) CDCI,. -40k 191
219 (cir)
- 131 22,314 207 (cis) CDCI,, -25°C 191
- I36 20,043 - CDCI,, - 2 5 2 191
-115.8 25,964 - CDCI,, - 50°C d 210
-235.7 30,537 250 Aatone, - 83'C i 216
- 88.4 20.585 276
-41.0 23.517 36.286 244 191

-40 23,682 36,408 241 191

- 39.0 22,364 36,722 191

- 109.4 18,600 - 250 ketone, - 6 0 ' ~ / 21 I. 230

- 141.6 14,960 6081 - ketone, - 6 0 ' ~ m 21 I
~~~~~~~

a 'J(SnSn)(Hz) in (Me,N),PO solution.

b ,J(SnSn) = 2043 Hz in (Me,N),FQ solution.
f ntd, Norbornadiene.
d I .5-cod. 1.5Cyclooctadicne.
8 SnCIJHgCI and the phosphines are mutually in trans positions.

3 2J('v9Hg"PSn), 41.479 Hz.

9 2J(1qgHg"*Sn),42.688 HI.
h 2J('99Hg11qSn), 39.916 Hz.
2J('99Hg"9Sn), 39.294 Hz.
' 6"'S.n values are dependent on SnCI, conantration; the observation of two signals is not accounted for.
k 2J("9Sn31P) (Hz) in CDCI,. -40'C.
I 'J(SnSn) not observed; the m n a n c a are observed only in the presence of other major specks.
m The value of I'J(SnSn)lis rather small for mutually trans positions of the SnCI, groups. although the value of IJ(19sPt13C)
(1794 Hz) points to a trans arrangement of "CO and CI.
 TABLE 26
Comparison of reduced couplings IK(Ex) (lozoNA-2 U I - ~ )for E = 13C, 2'Si, 'I'Sn, nnd 207Pb"

Compound X lJ(' I9SnX) ' K (1'9SnX) 'K ( ''CX) 'K(29SiX) 'K('07PbX)

+ 39.0 + 106.7'20
~~

Me,E-H 'H - 17441'9 +4.14'*' +7.69lz3

Me,E-BH, "B - 554'5 + 38.6 + 5.16' +9.6715 -
Me,E-CH, -34OZ2 + 30.2 +4.80342 + 8.313"~ +39.635'
Me3E-CH=CHMeb I3C -446.690 + 39.7 + + 10.7'" +56.8352
Me,E-C=C-H '3C -415.576 + 36.9 + 8.18 " + 14.276 - 9.34='59
Me,E-SiMe, 29Si + 65612 + 73.8 +9.53" + 17.9 -
Me3E-SnMe3 '19Sn +4 4 6 O 2 O 5 + 267.3 +38.8 54 +73.8" + 381.213
Me3E-N(Me)Ph I5N +2.213 +0.5 (+)3.37' 345 (+)3.47' 76 - 102.813
Me,E-PPh, ,'P + 596',O -32.9 - 1.20342 -2.22123 - 131.313
Me3E-SeCH3 77Se + 1015180 - 118.9 - 17.00 j4' -24.3h 348 -244.213
(Me3E)2Te lz5Te - 1385301 -97.9 - 8.5'346 - -
(Me,PhCCH,),E-F I9F +2298183 - 54.6 -9.3' 342 - 12.2" 349 -
[(Me3SiCH2)3Sn12Hg 199Hg ( -)6157'94 (+)771.3 + 128.5' 342 (+)228.5" "O -
195Pt
C~S-[P~(P~~E)P~-(PP~,)~] (-)12,686190 (+)1318 (+)91.5" 347 - ( +)34O3353
M~&W(C~)~(CSH~) 1 8 3 ~
- 150" + 80.5 (+)7.6" - -

'K(EX) = (4n2/h)(yEyx)-''J(EX).
* Cis compound.
Value for Et,Pb-C=C-H.
'Estimated from various values for compounds Me3Si-SiMe2R.
'Value for PhNHMe.
Value for Me3SiNC4H4.
Value for Me2.%.
' Value for (H,Si),Se.
Value for Me,Te.
' Value for Me,CF.
'Value for Me,SiF.
I Value for Me,Hg.
Value for [(Me,SiCH,)Me,Si],Hg.
" Value for cis-[PtPh,(PEt,),],.
 TABLE 27
Selected coupling coastants 1J('19Sn'3C), 2J(''9Sn'H), and 1J(119SaX)
of trimethyltin compounds (Me,SnX)

'J(''9Sn'3C),, zJ(119Sn'Hh,," 'J('19SnX)

Compound (H4 (H4 (H4 X Solvent Reference

Me,Sn-CH,b - 337.8 + 54.3 -337.8 13C 154

Me&-CH,Me - 320.8 + 52.8 -374.2 1% 154
Me,Sn-CHMe, - 306.7 + 50.8 -410.2 'JC 154
Me,Sn-CMe, -295.7 + 50.0 -436.9 13C 154
Me,Sn-CH(CH,), -341.6 - 502.8 1% 154
Me,Sn-CH(CH,), -313.5 - - 389.7 "C 154
Me,%-CH(CH,), -311.8 51.4 - 405.6 13C 154
Me,Sn-CH(CH,), - 303.9 + 50.8 -407.4 13C 154
(equatorial) -299.4 -403.8 13C CDzCl,, - 69°C 354
e
(axial) - 295.5 - CDZCI,, -69°C 354
t: Me&-CH,Bu' -318.6 - 369 154
Me,Sn-CH,SiMe, -331 - - 250 CDCI, 170
Me&-CH,SnMe, - 330 63.0 - 287 CDCI, 355
Me,Sn-CH(SnMe,), - 323 - - 192 CDCl, 243
Me&-C(SnMe,), -318 - 107 CDCI, 243
Me&-CH=CHMe
(cis) - 346.9 -464.6 "C CDCI, 90
(trans) - 352.0 - -478.4 13C CDCI, 90
Me,Sn-C6H, -347.5 + 54.6 -474.4 'JC CDCI, 356
Me,SnCH=C=CH, - 356.0 - - 382.0 13C - 354
(Me,Sn),C=C=C(SnMe,), - 344.0 - - 296.0 13C 248
Me$-C-C-Me -404.1 +60s - 502.9 13C C6D6 159
Me,SnC(CO,Et)N, -385.2 - -300 "C C6D6, 38°C 357
(Me3Sn)2CN2 -365 - -217 13C C6D6 275
(Me,Sn),CPMe, - 324.7 - nod '3C C6D6 233
Me+-SiMe, -245.8 + 46.7 + 656 29Si %% C6H6 12
 (Me,Sn),Si -261.0 +220 C6D6 212
Me,Sn-GeMe, 255.1 - ? 249
Me&-SnMe, - 244.2 +48.3 +4460 C6H6 205
Me,Sn-H -352 + 56.5 - 1744 CDCI, 162
Me,Sn-Cl -379.7 +58.1 - CC1, 358
Me,Sn-Br -368.9 + 57.8 CCI, 358
Me,Sn-OMe -398.0 + 57.8 CDCI, 249
Me,Sn-SCH, -355.8 +56.9 - - ? 249
Me,Sn-SeSnMe, - 340.0 +56.1 + 1060 77Se 80% CHZCI, 301
Me,Sn-NMe, -381.2 +55.3 - "N ? 249
Me3Sn-NEt, -378.8 + 55.2 <lC "N ? 249
Me&-N(SnMe,), - 366.2 79.6' "N C6D6 16
(Me,Sn),NN(SnMe,), - 349.6 - - - Toluene-d, 100
Me,Sn-P(SnMe,), -301.8 + 52.5 -833.7 ,'P C6D6 325
Me,Sn-As(Ph)SnMe, -283.2 - CDCI, 271
e Me,Sn-Bi(SnMe,), -220 +47.Or - C6D6 327
2 [Me&-BHJ -110 + 32.0' - 554 THF/C6D6 15
Me,Sn-B(NMe,), -230.4 +42.3 -953 Toluene-d, 15
Me,SnLi. 3THF + 155 -6.2 - 25% THF 151
cis-[Fe(CO),(SnMe,),] -214 CD,CI, 209
cis-[Ru(CO),(SnMe,),] -207 Neat 208
cis-[Os(CO),(SnMe,),] -278 CD,CI, 208

Data taken from reference 22 if not otherwise indicated.

* Various values for 1J(119Sn13C)are reported between 335 to 340 HZ.,~,
Reference 95.
no, Not observed.
'Direct "N measurement in C,D, (90%).76
*Reference 321.
Reference 15.
 TABLE 28
Selected coupling Eoast.Ilt8 (Hz) 1J(11'S~15C),
'J("'Sn'H), and lJ(ll'saX) of dimethyltin compollncls (Me,SoX,)
I J (119 2J(119Sn1Hh,,," 1J(119SnX)
Compound (H4 (Hz) (H4 X Solvent Reference

Me,Sn(CH3),' -337.8 + 54.3 - 337.8 13c - 154

Me,Sn(CH,Me), -302.5 +49.8 -354.7 I3C CDCI, 155
Me,Sn(CH,Bu'), -297.0 - - 346.0 3
c CDCI, 170
Me,Sn(CH,SiMe,), -325.0 - -246 I3C CDCI, 170
Me,Sn(CH,)4 -300.6 + 54.9 -334.8 I3C 154
Me,Sn(CH,), - 306.9 - -322.1 "C - 154
Me2Sn(CH2)6 -300.4 +51.3 - 339.7 13C - 154
Me,Sn(CH=CHMe),' -357.2 - (4 I3C CDCI, 90

Me2snmE
\=/
E
CMe, - 379.2 + 59Sd -440.0 "C C6D6 242
SiMe, - 354.0 +55Sd -470.0 3
c C6D6 242
SnMe, -349.0 +54.1d -495.6 "C C6D6 242
PPh -328.0 + 59Sd -438.0 "C C6D6 242
+61.0d
BNEt, - 355 + 59.0d -455 I3C C6D6 242
Me,Sn(C=C-H) - 501.2 + 70.0' -606.7' 3c C6D6 159
Me,Sn(SnMe,), - 179.4 - + 2873 Il9Sn 95% C6H6 167
Me,SnH, - + 58.0 - 1797.0 'H C6D6 76
Me,SnC1, -468.4 +68.2' ca4 358
Me,SnBr, -442.7 +66.7O CCI, 358
 - 368.7 +61.4h - - CDCI, 76
’
S
‘
(Me,SnS), -407.0 - - - CDCI, 76
(Me,SnW, - 360.0 +61.0‘ 1228 77Se ? 359
Me,Sn(NEt2)2 -472 + 59.4 - - CCl, 320
(Me,SnNEt), -430 - - - C6D6 76

Data taken from reference 22 if not indicated otherwise.

Various values for 1J(11gSn13C) are reported between 335 and 340 HZ.’~’
The cis,& isomer, 1J(’19Sn13C=), ranges from 480 to 494 Hz.
Reference 242.
Reference 95.
1 Reference 360 gives 5 0 4 4 9 4 Hz [1J(119Sn13C),,e]and 598 Hz [1J(119Sn13C=)];no solvent is reported.
0 Reference 358.
Reference 76.
‘
21
c
w
Reference 359.
1 74 BERND WRACKMEYER

TABLE 29
Some 1J(119Sn1SN)
data

Compound Solvent Reference

Me,Sn-NEt, < 1.0 C6D6 76

Me,Sn-NHPh -26.3 C6H6 12
Me,%-NMePh +2.2 C6H6 118
(Me,Sn),NBu' (-)38.0 C6D6 76
(Me,Sn),NPh -41.4 C6H6 118
(Me,Sn),NGeMe, (-)68.4 C6D6 76
(Me,Sn),N (-)79.6 C6D6 76
(Me,Sn),N-NMe, 46.0 C6D6 76

Me,Sn-N
3
Me,Sn-N( PMe,)Ph +9.5
6.4 C6D6

C6H6
76

118
Me,Sn-N[P(S)Me,]Ph -21.0 C6H6 118
Me,Sn(NMePh), +24.0 C6H6 118
MeSn(NMePh), +87.0 C6H6 118
[MeSn(OCH,CH,),N J, 75.6, 110.0 CDCI, 54
Bu'Sn(0CH ,CH ,),N 69.9 CDCI,, -20°C 54
Sn(NMePh), + 175.0 C6H6 118
Sn"(SiMe,),l, 344" C6D6,80°C 76

1J(119Sn14N)
= 245 10 Hz
 TABLE 30
Some J("'SnI3C) data for OrganotrimethyiStaMawswith a rigid geometry of the hydrocarbon framework

LJ(119SnL3C)Me 1J(L19Sn13C)
2J(L19Sn13C)3J(119Sn13C)
Number Compound" (H4 (Hz) (Hz) (H4 Footnotes Reference

Me&-chex (eq) 299.4 403.8 no 65.0 b, c 354

1-Me,Sn-4-Bd-chex (eq) 304.5 408.1 13.6 66.6 129
1-Me,Sn-4-Bu'-chex (ax) 301.3 402.5 12.0 13.8 129
1-Me,Sn-norbornane 3 13.8 459.0 17.3 (2,6) 51.9 (3.5) d 239
13.0 (7) 65.8 (4)
5 2-Me3Sn-norbornane (exo) 306.0 407.0 9.8 (1) 12.7 (4) d 146
23.4 (3) 67.4 (6)
- (7)
6 2-Me3Sn-norbornane (endo) 306.0 432.0 10.0 (1) 23.4 (4) b. d 146
no (3) 36 (6)
56.6 (7)
7 7-Me3Sn-norbornane 314.2 405.6 no 11.9(2,3) b, d 239
67.5 (5,6)
8 3-Me3Sn-nortricyclane 3 13.9 411.8 6.0 (2) 53.6 (1) d 239
12.4 (4) 9.7 (5)
8.0 (6)
57.8 (7)
9 7,7-(Me,Sn),-norcarane 3 18.0 332.0 24.0 34 (Sn,endo) 243
44 (Sn,exo)
 TABLE 30 (cont.)
1J(1'9Sn13C)Me 1J('19Sn13C) 2J(119Sn13C) 3J(119Sn13C)
Number Compound" (H4 (Ha (Hz) (H4 Footnotes Reference

10 1-Me3Sn-tricyclo[4. 1.1.02.7]heptane1 343 463.3 17.1 (2) no b, 4 e 244

21.5 (7)
11 1-Me3Sn-bicyclo[2.2.2]-octane 292 459 no 54 b, e 244
12 1-Me@-cubane 313.2 no 24.6 37.4 b, e 244
13 I-Me,Sn-adamantane 290.4 451.7 12.2 51.1 239
14 2-Me3Sn-adamantane 295.8 406.6 12.3 8.5 (4,9) d 164
60.0 (8, 10)
15 1-Me3Sn-4-Me-l,4-ethano- 312.5 no no (2) 50.8 (3) b 164
1,2,3,4tetrahydronapthalene 312.5 4.6 (9) 36.0 (10)
16 CMe,Sn-quinuclidine 307.0 no 9.0 46.0 b 128

Structure numbers correspond to the entries in Fig. 8; 3J(119Sn13C)against the dihedral angle 4.
no, Not observed, or not reported.
' CDZCIZ, -69°C.
' Numbers in parentheses indicate the positions of the carbon atoms.
'All values of J(SnI3C) are given as the average of 119/117Sn-13Ccoupling.'"
 Sn-NMR PARAMETERS 177

REFERENCES

1. P. J. Smith and L. Smith, Inorg. Chim. Acta Rev., 1973,7, 11.

2. J. D. Kennedy and W. McFarlane, Rev. Silicon, Germanium, Tin b a d Compd., 1974.1.235.
3. P. J. Smith and A. P. TupEiauskas, Annu. Rep. N M R Spectrosc., 1978,8,291.
4. J. D. Kennedy and W. McFarlane, in NMR and the Periodic Table (R. K. Harris and B. E.
Mann, eds.), Academic Press, London, 1978, p. 342.
5. R. Hani and R. A. Geanangel, Coord. Chem. Rev., 1982,44,229.
6. W. McFarlane, Annu. Rep. NMR Spectrosc., 1968, 1, 135.
7. W. McFarlane, Annu. Rep. NMR Spectrosc., 1972,5, 353.
8. A. G. Davies, P. G. Harrison, J. D. Kennedy, R. J. Puddephatt, T. N. Mitchell and
W. McFarlane, J . Chem. Soc. A, 1969, 1136.
9. P. G. Harrison, J. J. Zuckerman and S. E. Ulrich, J. Am. Chem. SOC.,1971,93,5398.
10. H.C. E. McFarlane, W. McFarlane and C . J. Turner, Mol. Phys., 1979,37, 1639.
1 I. A. Bax, Two-Dimensional Nuclear Magnetic Resonance in Lquiak, Delft Univ. Press, Delft,
1982, p. 50.
12. J. D. Kennedy, W. McFarlane, G. S. Pyne and B. Wrackmeyer, J. Chem. Soc., Dalton
Trans., 1975, 386.
13. J. D. Kennedy, W. McFarlane and B. Wrackmeyer, Inorg. Chem., 1976,15, 1299.
14. H. FuDstetter, H. Noth, B. Wrackmeyer and W. McFarlane, Chem. Ber., 1977,110,3172.
15. W. Biffar, H. Noth, H. Pommerening, R. Schwerthoffer, W. Storch and B. Wrackmeyer,
Chem. Ber., 1981,114,49.
16. R. R. Emst and W. A. Anderson, Rev. Sci. Instrum., 1966,37,93.
17. G. A. Morris and R. Freeman, J. Am. Chem. SOC.,1979,101,760.
18. D. M. Doddrell, D. T. Pegg, W. Brooks and M. R. Bendall, J . Am. Chem. SOC.,1981,103,
727.
19. D. T. Pegg, D. M. Doddrell and M. R. Bendall, J. Chem. Phys., 1982,77,2745.
20. 0 .W. SBrensen and R. R. Emst, J. Magn. Reson., 1983,51,477.
21. D. T. Pegg, D. M. Doddrell, W. M. Brooksand M. R.Bendal1.J. Magn. Reson., 1981,44,32.
22. V. S . Petrosyan, Prog. NMR Spectrosc., 1977, 11, 115.
23. E. W. Abel, S. K. Bhargava, K. G. Orrell and V. Sik, J. Chem. Soc., Dalton Trans., 1982,
2073.
24. A. Abragam, Principles of Magnetic Resonance, Oxford Univ. Press, London and New
York, 1961.
25. F. Noack, NMR: Basic Princ. Prog., 1978,3, 83.
26. L. G. Werbelow and D. M. Grant, Adv. Magn. Reson., 1977,9,83.
27. R. K. Harris, Nuclear Magnetic Resonance Spectroscopy, Pitman, London, 1983, p. 85.
28. J. Reisse, NATO Adv. Study Inst. 1983, 103,63-87, and references therein.
29. P. S . Hubbard, Phys. Rev., 1963,131, 1155.
30. J. H. Noggle and R. E. Schirmer, The Nuclear Overhauser E’ect, Academic Press, New
York, 1971.
31. R. R. Sharp,J. Chem. Phys., 1972,57,5321.
32. R. R. Sharp, J . Chem. Phys., 1974,60,1149.
33. Y.C. Puskar, T. A. Saluvere, E. T. Lippmaa, A. B. Permin and V.S . Petrosyan, Dokl. Akad.
Nauk SSSR, 1975,220, 112.
34. R. R. Sharp and J. W. Tolan, J. Chem. Phys., 1976,65,522.
35. C. R. Lassigne and E. J. Wells, Can. J. Chem., 1977,55,927.
36. C . R. G. Lassigne and E. J. Wells, J. Magn. Reson., 1977,26, 55.
37. S.J. Blunden, A. Frangou and D. G. Gillies, Org. Magn. Reson., 1982,20, 170.
38. G. R. Hays, D. G. Gillies, L. P. Blaauw and A. D. H. Claque, J. Magn. Reson., 1981,45,102.
178 BERND WRACKMEYER

39. N. F. Ramsey, Phys. Rev., 1950,78,689.

40. K. A. K. Ebraheem and G. A. Webb, Prog. N M R Spectrosc., 1978, 11, 149.
41. G. A. Webb, NATO Adv. Study Jnst. 1983,103,29,49.
42. J. A. Pople, Discuss. Faraday SOC.,1962, 34, 7.
43. J. A. Pople, J. Chem. Phys., 1962,37,60.
44. J. A. Pople, Mol. Phys., 1964,7,301.
45. M. Karplus and J. A. Pople, J. Chem. Phys., 1963,38,2803.
46. C. J. Jameson and H. S. Gutowsky, J. Chem. Phys., 1964,40, 1714.
47. J. Mason, Adv. Inorg. Chem. Radiochem., 1976, 18, 197.
48. J. Mason, Adv. Inorg. Chem. Radiochem., 1979,22, 199.
49. A. A. Cheremisin and H. P. Schastnev, J. Magn. Reson., 1980,40,459.
50. J. D. Kennedy, J. Mol. Srrucr., 1976,31,207.
51. J. D. Kennedy, J. Chem. Soc., Perkin Trans. 2, 1977,242.
52. K. Jurkschat, C. Miigge, A. Tuchach, A. Zschunke, M. F. Larin, V. A. Pestunovich and
M. G. Voronkov, J. Organomet. Chem., 1977,139,279.
53. V. K. Voronov, M. G. Voronkov, L. V. Baikalova, B. Z. Shterenberg, E. S. Domnina and
R. G. Mirskov, Izv. Akad. Nauk SSSR, Ser. Khim., 1978,1655.
54. K. Jurkschat, C. Miigge, T. Tzschach, A. Zschunke, G. Engelhardt, E. Lippma, M. Magi,
M. F. Larin, V. A. Pestunovich and M. G. Voronkov. J. Organomet. Chem., 1979,171,301.
55. K. Jurkschat, C. Miigge, A. Tzschach and A. Zschunke, Z. Anorg. Allg. Chem., 1980,463,
123.
56. W. W. du Mont and H. J. Kroth, Z. Naturforsch., E: Anorg. Chem., Org. Chem., 1980,35B,
700.
57. J. Otera, T. Hinoishi and R. Okawara, J. Organomet. Chem., 1980,202, C93.
58. J. Otera, J. Organomet. Chem., 1981,221, 57.
59. A. Tzschach and W. Uhlig, Z. Anorg. Allg. Chem., 1981,475,251.
60. J. Otera, T. Hinoishi, Y. Kawabe and R. Okawara, Chem. Lett., 1981,273.
61. S. J. Blunden, P. J. Smith and D. G. Gillies, Inorg. Chim. Acta, 1982,60, 105.
62. L. Korecz, A. A. Saghier, K. Burgler, A. Tzschach and K. Jurkschat, Inorg. Chim. Acra,
1982,58,243.
63. A. Tzschach, K. Kurkschat, A. Zschunke and C. Miigge, Z. Anorg. Allg. Chem., 1982,488,
45.
64. R. Conton, D. Dakternieks and C.-A. Harvey, Inorg. Chim. Acra, 1982,61, 1.
65. R. Colton and D. Daktemieks, Inorg. Chim. Acta, 1983,71, 101.
66. J. HoleEek, M. Nadvornik, K. Handlii and A. LyEka, J . Organomet. Chem., 1983,241,177.
67. J. Otera, T. Yano and K. Kusakabe, Bull. Chem. SOC.Jpn., 1983,56, 1057.
68. A. Zschunke, C. Miigge, N. Scheer, K. Jurkschat and A. Tzschach, J. Crysrallogr.
Spectrosc. Res., 1983, 13,201.
69. H. C. Clark, V. K. Jain, J. J. McMahon and R. C. Mehrotra, J. Organornet. Chem., 1983,
243,299.
70. H. Fujiwara, F. Sakai and Y. Sasaki, J . Chem. SOC.,Perkin Trans. 2,1983, 11.
71. A. G. Davies and A. J. Price, J. Organomet. Chem., 1983,258, 7.
72. J. Holekk, K. Handlii, M. Nadvomik and A. LyEka, J. Organomet. Chem., 1983,258, 147.
73. A Saxena and J. P. Tandon, Polyhedron, 1983,2,443.
74. M. F. Lappert, P. P. Power, M. J. Slade, L. Hedberg, K. Hedberg and V. Schomaker,
J. Chem. SOC.,Chem. Commun., 1979,369.
15. J. J. Zuckerman, Organomet. Coord. Chem. Germanium, Tin Lead, Plenary Lecr. Int. Conf.,
2nd, 1977, Abstracts, AS.
76. B. Wrackmeyer, unpublished results.
77. A. Bonny, A. D. McMaster and S. R. Stobart, Inorg. Chem., 1978,17,935.
 "'Sn-NMR PARAMETERS 179

78. P. Jutzi, F. Kohl, P. Hofmann, C. Kriiger and Y.-H. Tsay, Chem. Ber., 1980,113,757.
79. A. Almeningen, A. Haaland and T. Matzfeld, J. Organomet. Chem., 1967,7,97.
80. R. W. Rudolph, W. L. Wilson, F. Parker, R. C. Taylor and D. C . Young, J. Am. Chem. SOC.,
1978,100,4629.
81. B. S. Pons, D. J. Santure, R. C. Taylor and R. W .Rudolph, Electrochim. Acta, 1981,26,365.
82. R. W. Rudolph, W. L. Wilson and R. C. Taylor, J. Am. Chem. SOC.,1981,103,2480.
83. L. L. Lohr, Inorg. Chem., 1981,20,4229.
84. V. S. Lyubimov and S. P. Ionov, Russ. J. Phys. Chem. (Engl. Transl.), 1972,46,486.
85. S . P. Ionev and V. S. Lyubimov, Russ. J. Phys. Chem. (Engl.Transl.), 1972,54,5.
86. A. Rahm, M. Percyre, M. Petraud and B. Barbe, J. Organornet. Chem., 1977,139,49.
87. M. Pereyre, J. P. Quintard and A. Rahm, Pure Appl. Chem., 1982,54,29.
88. J. D. Kennedy and W. McFarlane, J. Chem. SOC.,Perkin Trans. 2, 1974, 146.
89. J. D. Kennedy, W. McFarlane and G. S. Pyne, Bull. SOC.Chim. Belg., 1975,84,289.
90. T. N. Mitchell and C. Kummetat, J. Organomet. Chem., 1978, 157,275.
91. B. Wrackmeyer, J . Organomet. Chem., 1978,145,183.
92. W. W. du Mont and H. J. Kroth, Angew. Chem., 1977,89,832; Angew. Chem., Int. Ed. Engl.,
1977, 16,792.
93. M. Drager, Z. Anorg. Allg. Chem., 1981,477, 154.
94. A. S. Secco and J. Trotter, Acta Crystallogr., Sect. C, 1983, C39,451.
95. B. Wrackmeyer, Rev. Silicon, Germanium, Tin Lead Compd., 1982,6, 75.
96. A. G. Davies, M. W. Tse, J. D. Kennedy, G. S. Pyne, W. McFarlane, M. F. C. Ladd and
D. C. Povey, J. Chem. SOC.,Perkin Trans. 2, 1981, 369.
97. C. J. Jameson, Bull. Magn. Reson., 1980,3,3.
98. J. D. Kennedy, W. McFarlane, P. J. Smith, R. F. M. White and L. Smith, J. Chem. SOC.,
Perkin Trans. 2, 1973, 1785.
99. T. N. Mitchell, Org. Magn. Reson., 1976,8, 34.
100. T. Gasparis-Ebeling, H. Noth and B. Wrackmeyer, J. Chem. SOC.,Dalton Trans., 1983,97.
101. J. P. Quintard, M. Degueil-Castaing, B. Barbe and M. Petraud, J. Organomet. Chem., 1982,
234,41.
102. J. P. Quintard, M. Degueil-Castaing, G. Dumartin, B. Barbe and M. Petraud, J. Organomet.
Chem., 1982,234,27.
103. S . KERSCHL,A. SEBALD AND B. WRACKMEYER; Org. Magn. Reson., 1985, in press.
104. G. A. Olah and L. D. Field, Organometallics, 1982, 1, 1485.
105. T. N. Mitchell, J. Organomet. Chem., 1983,255,279.
106. J. D. Kennedy, W. McFarlane and G. S. Pyne, J. Chem. SOC.,Dalton Trans., 1977,2332.
107. N. F. Ramsey, Phys. Rev., 1953,91,303.
108. H. M. McConnell, J. Chem. Phys., 1956,24,460.
109. J. A. Pople and D. P. Santry, Mol. Phys., 1964,8, 1.
110. C. J. Jameson and G. S. Gutowsky, J . Chem. Phys., 1969,51,2790.
11 1. M. Barfield and M. Karplus, J. Am. Chem. Soc., 1969,91, I .
112. A. C. Blizzard and D. P. Santry, J. Chem. Phys., 1971,55,950.
113. J. Kowalewski, Annu. Rep. N M R Spectrosc., 1982, 12, 81.
114. J. A. Pople, J. W. McIver and N. S. Ostlund, J. Chem. Phys., 1968,49,2960,2965.
115. J. Kowalewski, Prog. N M R Spectrosc., 1977, 11, 1.
116. P. Pykko and L. Wiesenfeld, Mol. Phys., 1981,43, 557.
117. P. Pykko, J. Organomel. Chem., 1982,232,21.
118. J. D. Kennedy, W. McFarlane, G. S. Pyne and B. Wrackmeyer, J. Organomet. Chem., 1980,
195, 285.
119. N. Flitcroft and H. D. Kaesz, J. Am. Chem. Soc., 1963.85, 1377.
120. C. Schumann and H. Dreeskamp, J. Magn. Reson., 1970,3,204.
180 BERND WRACKMEYER

121. S. E. Ulrich and J. J. Zuckerman, Inorg. Chim. Acta, 1979,34, 161.

U2. J. Dufermont and J. C. Maire, J. Organomet. Chem., 1967,7,415.
123. H. Marsmann, NMR: Basic Princ. Prog., 1981, 17, 1.
124. H. A. Bent, Chem. Rev., 1961,61,275.
125. M. Bullpitt, W. Kitching, W. Adcock and D. Doddrell, J. Organornet. Chem., 1976, 116,
161.
126. D. L. Lichtenberger and T. L. Brown, J. Am. Chem. SOC.,1977,99,8187.
127. G . Matsubayashi and J. Iyoda, Bull. Chem. ,Sot. Jpn., 1977,50,3055.
128. K. B. Becker and C. A. Grob, Helv. Chim. Acfa., 1978,61,2596.
129. J. S.Filippo, J. Silbermann and P. J. Fagan, J. Am. Chem. Soc., 1978,100,4834.
130. G. D o m e t i s , R. J. Magee and B. D. James, J. Organomet. Chem., 1978,148,339.
131. K. Kamienska-Trela, J. Organomet. Chem., 1978,159, 15.
132. D. J. Cane, W. A. G. Graham and L.Vancea, Can.J. Chem., 1978.56, 1538.
133. D. Hanssgen and E. Odenhausen, Chem. Ber., 1979,112,2389.
134. T. Birchall and J. P. Johnson, Can.J . Chem., 1979,57, 160.
135. G. Domazetis, R. J. Magee and B. D. James, J. Organomet. Chem., 1979,173,357.
136. K. von Werner, H. Blank and K. Yasufuku, J . Organomet. Chem., 1979,165,187.
137. A. Gambaro, V. Peruzzo, G. Plazzogna and G. Tagliavini, J. Organomet. Chem., 1980,197,
45.
138. B. Mathiasch, J. Organomet. Chem., 1980,19437.
139. M. J. Vaickus and D. G. Anderson, Org. Magn. Reson., 1980,14,278.
140. D. E. Axelson, C. E. Holloway and C. P. J. Vuik, Org. Magn. Reson., 1980,14,220.
141. M. Drager and H. J. Guttmann, J. Organomet. Chem., 1981,212,171.
142. G . Domazetis, ,R. J. Magee and B. D. James, J. Inorg. Nucl. Chem., 1981,43, 1351.
143. B. Mathiasch, Org. Magn. Reson. 1981,17,296.
144. M. J. Cuthbertson and P. R. Wells, J. Organomet. Chem., 1981,216,339.
145. A. D. McMaster and S . Stobart, J. Am. Chem. Soc., 1982,104,2109.
146. W. Kitching, Org. Magn. Reson., 1982,20, 123.
147. K.Jurkschat and M. Gielen, Bull. SOC.Chim. Belg., 1982,91,803.
148. K. Jurkschat and M. Gielen, J. Organomet. Chem., 1982, u6,69.
149. U. Weber, N. Pauls, W. Winter and H. B. Stegmann, Z. Naturforsch., B: Anorg. Chem., Org.
Chem., 1982,37B, 1316.
150. H. G. Kuivila, T. J. Karol and K.Swami, Organomefallics, 1983,2,909.
151. J. D. Kennedy and W. McFarlane, J . Chem. SOC.,Chem. Commun., 1974,983.
152. D. Steinborn, R. Taube and R. Radeglia, J. Organomet. Chem., 1982,229,159.
153. D. Steinborn, M. Buthge, R. Taube, R. Radeglia, K. Schlothauer and K. Nowak,
J . Organomef. Chem., 1982,234,277.
154. H. G. Kuivila, J. L. Considine, R. H. Sarma and R. J. Mynott, J . Organomef.Chem., 1976,
111, 179.
155. B. Wrackmeyer, Specrrosc.: Int. J., 1982, 1,201.
156. T. N. Mitchell, J . Organomet. Chem., 1977, 141,289.
157. B. Wrackmeyer, J. Organornet. Chem., 1979,166,353.
158. F. Hold and B. Wrackmeyer, J. Organomet. Chem., 1979,179,397.
159. B. Wrackmeyer, J. Magn. Reson., 1981,42,287.
160. W. McFarlane, J . Chem. Soc., A, 1967,528.
161. B. Wrackmeyer, Z. Naturforsch., B: Anorg. Chem., Org. Chem., 1982,37, 1524.
162. T. N. Mitchell, J. Organornet. Chem., 1973,59, 189.
163. T. N. Mitchell and G. Walter, J . Organomet. Chem., 1976, 121, 177.
164. W. Kitching, G. Drew, W. Adcock and A. N. Abeywickrema, J. Org. Chem., 1981,46,2252.
165. E. Matarosso-Tchiroukhine and P. Cadiot, Can. J. Chem., 1983,61,2476.
 119Sn-NMR PARAMETERS 181

166. J. D. Kennedy and W. McFarlane, J. Chem. SOC.,Dalton Trans., 1976, 1219.

167. T. N. Mitchell and G. Walter, J. Chem. SOC.,Perkin Trans. 2, 1977, 1842.
168. A. Blecher, B. Mathiasch and T.N. Mitchell, J. Orgunomet. Chem., 1980,184, 175.
169. T. N. Mitchell and M. El-Behairy, Helv. Chim. Acta, 1981,64,628.
170. T. N. Mitchell, A. Amamria, B. Fabisch, H. G. Kuivila, T. J. Karol and K. Swami,
J . Orgunornet. Chem., 1983,259, 157.
171. R. W:Rudolph, R. L. Voorkees and R.E. Cochoy, J. Am. Chem. SOC.,1970,92,3351.
172. R. E. Loffredo and A. D. Norman, J. Am. Chem. SOC.,1971,93,5587.
173. K. S.Wong and R. N. Grimes, horg. Chem., 1977,16,2053.
174. M. L.Thompson and R. N. Grimes, Inorg. Chem., 1972,11,1925.
175. W. McFarlane and D. S. Rycroft, J. Chem. SOC.,Dalton Truns., 1974, 1977.
176. M. Drager and B. Mathiasch, Angew. Chem., 1981,93,1079.
177. H. Schumann and H. J. Kroth, Z. Naturforsch., B: Anorg. Chem., Org. Chem., 1977,32,876.
178. H. Schumann and W. Feldt, Z. Anorg. A&. Chem., 1979,458,257.
179. P. A. W. Dean, D. D. Phillips and L. Polensek Can. J. Chem., 1981,s. 50.
180. J. D. Kennedy and W. McFarlane, J. Chem. Soc., Dulron Trans., 1973,2134.
181. P. A. W. Dean, Can. J. Chem., 1982,60,2921.
182. J. J. I. Arsenault and P. A. W.Dean, Can. J. Chem., 1983,61,1516.
183. W. McFarlane and R. J. Wood, J. Orgunornet. Chem., 1972,40, C17.
184. J. W. Emsley, L.Phillips and V. Wray, Prog. NMR Spectrosc., 1977,10,716-723.
185. P.A. W. Dean and D. F. Evans, J. Chem. Soc. A , 1968,1154.
186. R. 0.Ragsdale and B. B. Stewart, horg. Chem., 1965,4,740.
187. J. E. Drake and N. P. C. Westwood, J. Chem. SOC.A , 1971,3300.
188. B. N. Chernysov, N. A. Didenko and E. G. Ippolitov, Koord. Khim., 1983,9,210.
189. K. H. A. 0.Starzewski and P. S. Pregosin, Adv. Chem. Ser., 1982, I%, 23.
190. S. Carr, R.Colton and D. Dakternieks, J. Orgunomet. Chem., 1983,249,327.
191. K.H. A. 0.Starzewski, P. S. Pregosin and H. Ruegger, Helv. Chim. Actu, 1982,66,785.
192. A. Albinati, R. Naegli, K. H. A. 0.Starzewski, P. S.Pregosin, and H. Ruegger, Inorg. Chim.
Actu, 1983,76, L231.
193. J. R. Shapely and J. A. Osborn, Acc. Chem. Res., 1974,%, 76.
194. Yu.K. Grishin, V. A. Roznyatovskii, U. A. Ustynyuk, M. N. Bochkarev, G. S. Kalinina
and G. A. Razuvaev, Izv. Akad. Nuuk. SSSR, Ser. Khim., 1980,2190.
195. C. J. Jameson, J. Am. Chem. Soc., 1969,91,6232.
196. J. A. Pople and A. A. Bothner-By, J. Chem. Phys., 1965,42,1339.
197. G . Barbieri, R.Benassi and F. Taddei, J. Orgunornet. Chem., 1977,129,27.
198. L.Lunazzi and F. Taddei, Spectrochim. Actu, Part A , 1969,25A, 61 I .
199. P. G. Hamson, S. E. Ulrich and J. J. Zuckennan, horg. Nucl. Chem. Lett., 1971,7,865.
200. J. F. Almeida, H. Azizian, C. Eaborn and A. Pidcock, J. Organornet. Chem., 1981,210,121.
201. K. H. A. 0.Starzewski, H.Ruegger and P. S. Pregosin, Inorg. Chim. Acta, 1979,36, L445.
202. H. C. Clark, A. B. Goel and C. Billard, J. Organornet. Chem., 1979,182,431.
203. F. J. Weigert and J. D. Roberts, J. Am. Chem. SOC.,1969,91,4940.
204. B. Wrackmeyer, J. Mugn. Reson., 1984,59,141..
205. W. McFarlane, J. Chem. SOC.A , 1968, 1630.
206. D. F. Ewing, Annu. Rep. NMR Spectrosc., 1976,6A, 389.
207. B. Wrackmeyer, J. Organornet. Chem., 1978,148, 137.
208. L.Vancea, R. K. Pomeroy and W. A. G. Graham, J. Am. Chem. SOC.,1976,98, 1407.
209. R. K. Pomeroy, L. Vancea, H. P. Calhoun and W. A. G. Graham, Inorg. Chem., 1977,16,
1508.
210. M. Kretschmer, P. S. Pregosin and H. Riiegger, J. Organornet. Chem., 1983,241,87.
21 1. G. K. Anderson, H. C. Clark and J. A. Davies, Inorg. Chem., 1983,22,427.
182 BERND WRACKMEYER

212. W. Biffar, T. Gasparis-Ebeling, H. Noth, W. Storch and B. Wrackmeyer, J. Magn. Reson.,

1981.44.54.
213. W. McFarlane, unpublished observation.
214. B. Wrackmeyer, unpublished observations.
215. P. S. Pregosin and S. N. Sze,Helv. Chim. Acta, 1978.61, 1848.
216. B. R. Koch, G. V. Fazakerley and E. Dijkstra, Inorg. Chim. Acta, 1980,45, L51.
217. J. H. Nelson, V. Cooper and R. W. Rudolph, Inorg. Nucl. Chem. Left.,1980,16,263; ibid.,
587.
218. K. H. A. 0. Starzewski and P. S.Pregosin, Angew. Chem., 1980.92.323.
219. H. Moriyama, T. Aoki, S. Shinoda and Y. Saito, J . Chem. SOC.,Dulfon Trans., 1981,639.
220. C. R. Lassigne, E. J. Wells, L. J. Farrugia and B. R. James, J . Magn. Reson., 1981,43,488.
221. L. J. Farrugia, B. R. James, C. R. Lassigne and E.J. Wells, Inorg. Chim. Acta, 1981, 53,
L261.
222. H. Moriyama, T. Aoki, S. Shinoda and Y. Saito, J . Chem. SOC.,Chem. Commun., 1982,500.
223. R. J. Goodfellow and J. R. Herbert, Inorg. Chim. Acfa, 1982,65, L161.
224. N. W. Alcock and J. H. Nelson, J. Chem. SOC.,Dalfon Trans., 1982,2415.
225. M. C. Grossel, R.P. Moulding and K. R. Seddon, Inorg. Chim. Acfa Letf., 1982,64, L275.
226. J. H. Nelson and N. W.Alcock, Inorg. Chem., 1982,21, 1196.
227. L. J. Farrugia, B. R. James, C. R. Lassigne and E.J. Wells, Can. J. Chem., 1982,60,1304.
228. M. Kretschmer, P. S.Pregosin, P. Favre and C. W. Schlaepfer, J. Organornet. Chem., 1983,
253, 17.
229. M. Kretschmer, P. S. Pregosin and M. Garralda, J. Organomef. Chem., 1983, 244, 175.
230. G . K. Anderson, H. C. Clark and J. A. Davies, Inorg. Chem., 1983,22,434.
231. A. Albinati, P. S. Pregosin and H.Riieggen, Angew. Chem., 1984,%, 63.
232. A. B. Goel and S . Goel, Inorg. Chim. Acfa, 1984,82,41.
233. H. Schmidbaur, J. Eberlein and W. Richter, Chem. Eer., 1977,110,677.
234. S . J. Ruzicka and A. E. Merbach, Inorg. Chim. Acta, 1977,22, 191.
235. C. Miigge, H. Weichmann and A. Zschunke, J. Organomet. Chem., 1980,192.41.
236. T. D. Coyle, S. L. Stafford and F. G. A. Stone, Spectrochim. Actu, 1961,17,968.
237. H. C. Clark, N. Cyr and J. H. Tsai, Can. J. Chem., 1967,45, 1073.
238. M. Karplus, J. Chem. Phys., 1959,30,11.
239. D. Doddrell, J. Burfitt, W. Kitching, M. Bullpitt, C. H. Lee, R. J. Mynott, J. L. Considine,
H. G. Kuivila and R. H. Sarma, J. Am. Chem. SOC.,1974,%, 1640.
240. B. Wrackmeyer, Z. Naturforsch., B Anorg. Chem., Org. Chem., 1979,34B, 235.
241. T. N. Mitchell and A. Amamria, J. Organomet. Chem., 1983,252,47.
242. H. 0. Berger, H.Noth and B. Wrackmeyer, Chem. Eer., 1979,112,2866.
243. T. N. Mitchell and M. El-Behairy, J. Organomef.Chem., 1979,172,293.
244. E. W. Della and H. K. Patney, Ausf.J. Chem., 1979,32,2243.
245. B. Wrackmeyer, J. Organomef.Chem., 1981,205, 1.
246. G. Menz and B. Wrackmeyer, Z . Naturforsch., E: Anorg. Chem., Org. Chem., 1977,32B,
1400.
247. D. Doddrell, M. L. Bulpitt, C. J. Moore, C. W. Fong, W. Kitching, W. Adcock and B. D.
Gupto, Tetrahedron Len., 1973,665.
248. B. Wrackmeyer, J. Mugn. Reson., 1980,39,359.
249. M. E. Bishop, C. D. Schaeffer and J. J. Zuckerman, J. Organomef. Chern., 1975,101, C19.
250. S. J. Blunden, P. J. Smith, P. J. Beynon and D. G. Gillies, Carbohydr. Res., 1981,88,9.
251. T. N. Mitchell, personal communication.
252. P. Galow, A. Sebald and B. Wrackmeyer, J. Organomet. Chem., 1983,259,253.
253. A. Sebald, Dissertation, University of Munich, 1983.
254. H. J. Kroth, H. Schumann, H. G. Kuivila, C. D. Schaeffer and J. J. Zuckerman, J. Am.
Chem. SOC.,1975,97,1754.
 '"Sn-NMR PARAMETERS 183

255. C. Grugel, M. Lehnig, W. P. Neumann and J. Sauer, Tetrahedron Lett., 1980, 273.
256. W. Adcock, G. B. Kok, A. N. Abeywickrema, W. Kitching, G. M. Drew, H. A. Olszowy and
J. Schot, J. Am. Chem. Soc., 1983,105,290.
257. J. P. Quintard, M. Degueil-Castaing, G. Dumartin, A. Rahm and M. Pereyre, J. Chem. Soc.,
Chem.Commun., 1980, 1004.
258. J. D. Kennedy, J . Orgunomet. Chem., 1976,104,311.
259. B. Jousseaume, J. G. Duboudin and M. Petraud, J. Orgunomet. Chem., 1982,238, 171.
260. D. H. Harris, M. F. Lappert, J. S. Poland and W. McFarlane, J . Chem. Soc., Dulfon Trans.,
1975, 311.
261. V. N. Torocheshnikov, A. P. Tuptiauskas and Yu.A. Ustynyuk, J. Orgunomet. Chem.,
1974,81, 351.
262. A. P. Tuptiauskas, N. M. Sergeyev and Yu.A. Ustynyuk, Lief.Fiz. Rinkinys, 1971,11,93.
263. B. Wrackmeyer, Orgunomefullics, 1984,3, 1.
264. T. N. Mitchell, Org. Mugn. Reson., 1975,7,610.
265. N. P. Erchak, A. R. Ashmane, Yu.Yu.Popelis and E. Lukerits, Zh. Obshch. Khim., 1983,
53, 383.
266. E. Lukevits, 0.A. Pudova, Yu.Popelisand N. P. Erchak, Zh. Obshch. a i m . , 1981,51,115.
267. F. H. Kohler and N. Hertkorn, Z. Nuturforsch., B: Anorg. Chem., Org. Chem., 1983,38,407.
268. T. N. Mitchell and A. Amamria, J. Orgunomet. Chem., 1983,256,37.
269. B. Wrackmeyer, J. Orgunornet. Chem., 1980,190,237.
270. C. Bihlmayer and B. Wrackmeyer, Z. Nuturforsch., B: Anorg. Chem., Org. Chem., 1981,
36B, 1265.
271. B. Wrackmeyer and C. Bihlmayer, J. Chem. Soc., Chem. Commun., 1981, 1093.
272. B. Wrackmeyer, C. Bihlmayer and M. Schilling, Chem. Ber., 1983,116,3182.
273. B. Wrackmeyer and C. Bihlmayer, J. Orgunomef. Chem., 1984,%,33.
274. B. Wrackmeyer, Z. Nuturforsch., B Anorg. Chem., Org. Chem., 1978,33B, 385.
275. E. Glozbach and J. Lorberth, J. Orgunomet. Chem., 1980,191,371.
276. F. H. Kohler and W. A. Geike, J. Mugn. Reson., 1983,53, 297.
277. W. McFarlane, J. C. Maire and M. Delmas, J. Chem. Soc., Dulfon Trans., 1972, 1862.
278. B. K. Hunter and L. W. Reeves, Con. J. Chem., 1968.46, 1399.
279. A. P. Tuptiauskas, N. M. Sergeyev and Yu.A. Ustynyuk, Org. Mugn. Reson., 1971,3,655.
280. W. Kitching, H. A. Olszowy and G. M. Drew, Orgunometullics, 1982, 1, 1244.
281. J. J. Burke and P. C. Lauterbur, J. Am. Chem. SOC.,1961,83,326.
282. G. Dumartin, J.-P. Quintard and M. Pereyre, J. Orgunornet. Chem., 1980, 185, C34.
283. J.-P. Quintard, B. Elissondo and M. Pereyre, J . Orgunomet. Chem., 1981,212, C31.
284. C. J. Jameson, J. Am. Chem. Soc., 1969,91,6232.
285. M. Gielen, Bull. SOC.Chim. Belg., 1983,92,409.
286. H. Schumann, G. Rodewald, V. Rodewald, J. L. Lefferts and J. J. Zuckerman,
J . Orgunomet. Chem., 1980,187,305.
287. S. W. Carr, R. Conton, D. Dakternieks, B. F. Hoskins and R. J. Steen, Inorg. Chem., 1983,
22,3700.
288. J. D. Kennedy, W. McFarlane, G. S. Pyne, P. L. Clarke and J. L. Wardell, J . Chem. Soc.,
Perkin Trans. 2, 1975, 1234.
289. L. Verdonk and G. P. van der Kelen, J. Orgunomet. Chem., 1972,40, 139.
290. A. G. Davies, M. W. Tse, J. D. Kennedy, W. McFarlane, G. S. Pyne, M. F. C. Ladd and
D. C. Povey, J. Chem. SOC.,Chem. Commun., 1978,791.
291. B. Wrackmeyer, J. Orgunornet. Chem., 1978,153, 153.
292. S. Kerschl and B. Wrackmeyer, Z. Nuturforsch., B Anorg. Chem., Org. Chem., 1984,39,1037.
293. B. Wrackmeyer, J. Orgunomef.Chem., 1977,132,213.
294. P. E. Potter, L. Pratt, and G. Wilkinson, J. Chem. SOC.,1964,524.
295. M. R. Kula, E. Amberger and H. Rupprecht, Chem. Ber., 1965,98,629.
184 BERND WRACKMEYER

296. E. Amberger, H. P. Fritz, C. G. Kreiter and M. R. Kula, Chem. Ber., 1963,%, 3270.
297. J. R. Webster and W. L. Jolly, Inorg. Chem., 1971, 10, 877.
298. E. V. van den Berghe and G. P. van der Kelen, J. Organomet. Chem., 1971,26,207.
299. A. LyEka, D. h o b l , K. Handlii, J. Holefek and M. Nidvornik, Collect. Czech. Chem.
Commun., 1981,46,1383.
300. H. M. M. Yeh and R. A. Geanangel, Inorg. Chim. Acta, 1981,52,113.
301. J. D. Kennedy and W. McFarlane, J. Organornet. Chem., 1975,94,7.
302. A. P. TupEiauskas, Liet. Fiz. Rinkinys, 1977,17,233.
303. R. Kcister, personal communication, 1983.
304. P. J. Smith, R. F. M. White and L. Smith, J. Organomet. Chem., 1972,40,341.
305. F. A. K. Nasser and J. J. Zuckerman, J. Organomet. Chem., 1983,244,17.
306. E. V. van den Berghe and G. P. van der Kelen, J. Mol. Struct., 1974, u),147.
307. A. G. Davies and J. A. A. Hawari, J. Chem. SOC.,Perkin Trans. I , 1983,875.
308. S.David, A. Thidffry and A. Forchioni, Tetrahedron Lett., 1981,2647.
309. S. David, C. Pascard and M. Cesario, Nouv. J. Chim., 1979,3,63.
310. A. G. Davies, J. A. A. Hawari and P. Hua-De, J. Organomet. Chem., 1983,251,203.
31 1. H. Puff, W. Schuh, R. Sievers, W. Wild and R.Zimmer, J. Organomet. Chem., 1984,260,
271.
312. S. Masamune, L. R. Sita and D. J. Williams, J. Am. Chem. SOC.,1983,105,630.
313. F. W. B. Einstein, C. H. W. Jones, T. Jones and R. D. Sharma, Can.J. Chem., 1983,61,2611.
314. 3. Wrackmeyer, 2. Naturforsch., B: Anorg. Chem., Org. Chem., 1979 34B, 1464.
315. H. Puff, E. Friedrichs, R. Kundt and R.Zimmer, J. Orgunomet. Chem., 1983,259.79.
316. M. Grenz and W. W. du Mont, J. Organomet. Chem., 1983,241, C5.
317. W. W. du Mont and M. Grenz, 2. Naturforsch., B Anorg. Chem., Org. Chem., 1983,38B,
113.
318. W. W. du Mont and M. Grent, Chem. Ber. 1985,118,1045.
319. T. N. Mitchell and H. C. Marsmann, unpublished.
320. E. V. van den Berghe and G. P. van der Kelen, J. Orgunomet. Chem., 1973,61, 197.
321. M. Birkhahn, R. Hohlfeld, W. Massa, R.Schmidt and J. Lorberth, J . Organornet. Chem.,
1980,192,47.
322. E. V. van den Berghe and G. P. van der Kelen, J. Organomet. Chem., 1974,82,345.
323. W. Storch and B. Wrackmeyer, unpublished.
324. H. FuDstetter and H. Noth, Chem. Ber., 1979,112,3672.
325. J. P. van Lindhoudt, E. V. van den Berghe and G. P. van der Kelen, Spectrochim. Acta,
Part A, 1980, %A, 17.
326. M. Meissner, H. J. Kroth, K.-H. Kohricht and H. Schumann, Z . Naturforsch., B: Anorg.
Chem., Org. Chem., 1981,36B, 904.
327. G. Becker and M: Rossler, 2. Naturforsch., B Anorg. Chem., Org. Chem., 1982,37,91.
328. A. Schmidpeter, personal communication.
329. W. W. du Mont and B. Neudert, Z . Anorg. Allg. Chem., 1978,441,86.
330. H. Elser and H. Dreeskamp, Ber. Bunsenges. Phys. Chem., 1969,73,619.
331. T. N. Mitchell, J. Organomet. Chem., 1974,70, C1.
332. M. J. Cuthbertson and P. R. Wells, J. Organornet. Chem., 1981,216,349.
333. T. N. Mitchell and M. El-Behairy, J. Organomet. Chem., 1977,141,43.
334. B. Wrackmeyer, unpublished observations, 1980.
335. J. Meunier-Piret, M. van Meerssche, M. Gielen and K. Jurkschat, J. Organomet. Chem.,
1983,252,289.
336. M. Driiger, B.Mathiasch, L. Ross and M. Ross, Z . Anorg. Allg. Chem., 1983,506,99.
337. B. Mathiasch and T. N. Mitchell, J. Organornet. Chem., 1980,185,351.
338. S . C. Critchlow and J. D. Corbett, J. Am. Chem. SOC.,1983,105,5715.
 "Sn-NMR PARAMETERS 185

339. J. D. Kennedy and W. McFarlane, J . Chem. SOC.,Chem. Commun., 1974,983.

340. K. Kobayashi, M. Kawanisi, S. Kozima, T. Hitomi, H. Iwamura and T. Sugawara,
J. Organornet. Chem., 1981,217, 315.
341. J. D. Koola and U. Kunze, Inorg. Chim. Acta, 1983,76, L283.
342. J. B. Stothers, Carbon-13 Nuclear Magnetic Resonance Spectroscopy, Academic Press, New
York, 1972.
343. V. Wray, Prog. NMR Spectrosc., 1979,13, 177.
344. B. Wrackmeyer and W. Biffar, Z. Naturforsch., B: Anorg. Chem., Org. Chem., 1979, MB,
1270.
345. T. Bottin-Strzalko, M. J. Pouet and M. P.Simonnin, Org. Magn. Reson., 1976,8, 120.
346. W. McFarlane, Mol. Phys., 1967,12,243.
347. B. E. Mann and B. F. Taylor, I3C-NMR Data for Organometallic Compoundr, Academic
Press, London, 198I.
348. G. Pfisterer and H. Dreeskamp, Ber. Bunsenges. Phys. Chem., 1969,73,654.
349. R. K. Harris and B. J. Kimber, J. Magn. Reson., 1975,17, 174.
350. M. J. Albright, T. F. Schaaf, A. K. Hovland and J. P. Oliver, J. Organornet. Chem., 1983,
259, 37.
351. W. McFarlane, Mol. Phys., 1967, 13, 587.
352. T. N. Mitchell and H. C. Marsmann, Org. Magn. Reson., 1981, 15,263.
353. S . Carr, R.Colton and D. Dakternieks, J. Organomet. Chem., 1982,240, 143.
354. W. Kitching, D. Doddrell and J. B. Grutzner, J. Organomet. Chem., 1976,107, C5.
355. T. J. Karo, J. P. Hutchinson, J. R. Hyde, H. G. Kuivila and J. A. Zubieta, Organometallics,
1983,2, 106.
356. C. D. Schaeffer, S.E. Ulrich and J. J. Zuckerman, Inorg. Nucl. Chem. Lett., 1978,14,55.
357. R. Griining, P.Krommes and J. Lorberth, J. Organornet. Chem., 1977,127, 167.
358. V. S. Petrosyan, A. B. Pernin and 0. A. Reutov, J. Magn. Reson., 1980,40, 511.
359. M. Drager, B. Mathiasch and A. Blecher, Fresenius' Z. Anal. Chem., 1980,304,268.
360. V. A. Pestunovich, E. 0.Tsetlina, M. G. Voronkov, E. E. Liepin'sh, E. T. Bogoradovskii,
V. N. Cherkasov, V.S.Zavgorodnii and A. A. Petrov, Izv. Akad. Nauk SSSR, Ser. Khim.,
1979,694.
361. C. E. Michelson and R.0. Ragsdale, Inorg. Chem., 1970, 9, 2718.
362. W. W. du Mont, J. Organomet. Chem., 1978,153, C11.
363. R. W. Kunz, Helv. Chim. Acta, 1980,63,2054.
364. J. P. Quintard, B. Elissondo and D. Mouko-Mpegna, J. Organomet. Chem., 1983,251,175.
365. D. Dakternieks. R. W. Gable and G. Winter, Inorg. Chim. Acta, 1983,75, 185.
366. B. Wrackmeyer, J. Magn. Reson., 1985,61,536.
367. C. T. G. Knight and A. E. Merbach, Inorg. Chem., 1985,24,576.
368. N. S. Hosmane, N. N. Sirmokadam and R. H. Herber, Organometallics, 1984,3, 1665.
369. D. W. Allen, D. J. Derbyshire, J. S. Brooks, S.J. Blunden and P.J. Smith, J. Chem. SOC.
Dalton Trans., 1984, 1899.
370. C. S. Frampton, R. M. G. Roberts, J. Silver, J. F. Warmsley and B. Yavari, J. Chem. SOC.
Dalton Trans., 1985, 169.
371. D. Young, W. Kitching and G. Wickham, Aust. J. Chem., 1984,37,1841.
372. T . N. Mitchell and B. Fabisch, J. Organomet. Chem., 1984,269,249.
373. D. W. Hawker and P. R. Wells, Org. Magn. Reson., 1984,22,280.
374. D. W. Hawker and P. R. Wells, J. Organomet. Chem., 1984,266,37.
375. H. Schumann and R. Mohtachemi, Z. Narurforsch., B, Anorg. Chem., Org. Chem., 1984,39,
798.
376. T. N. hlitchell, H. Killing, R. Dicke and R. Wickenkamp, J. Chem. SOC.Chem. Commun.,
1985,354.
186 BERND WRACKMEYER

377. H. Killing and T. N. Mitchell, Orgunomerullics, 1984,3, 1318.

378. A. Albinati, P. S. Pregosin and H. Ruegger, Inorg. Chem., 1984,23,3223.
379. M. S. Holt, J. J. MacDougall, F. Mathey and J. H. Nelson, Inorg. Chem., 1984,23,449.
380. H. Moriyama, P. S. Pregosin, Y. Saito and T. Yamakawa, J. Chem. SOC.Dalton Trans., 1984,
2329.
381. P. S. Pregosin and H. Ruegger, Inorg. Chim. Actu, 1984,86,55.
382. M. Gielen and K. Jurkschat, J. Orgunornet. Chem., 1984,273,303.
383. M. Nadvornik, J. Holecek, K. Handlir and A. Lycka, J. Orgunornet. Chem., 1984,275,43.
384. K. B. Dillon and A. Marshall, J. Chem. SOC.Dalton Trans., 1984,1245.
385. K. Swami, J. P. Hutchinson, H. G. Kuivila and J. A. Zubieta, Orgunometullics, 1984,3,1687.
386. J. Otera, T. Yano, E. Kunimoto and T. Nakuta, Orgunometullics, 1984,3,426.
387. S . J. Blunden and R. Hill, Inorg. Chim. A m , 1984,87,83,
388. S . J. Blunden, R. Hill and D. G. Gillies, J. Orgunornet. Chem., 1984,270,39.
389. R. K. Harris, K.J. Packer and P. Reams, J. Mugn. Reson., 1985,61,564.
390. U. R. Kunze, J. Orgonomet. Chem., 1985,281,79.
391. A. Tzschach, M. Scheer and K. Jurkschat, Z. Anorg. Allg. Chem., 1984,508,73; 512, 177.
392. S. J. Blunden, P. A. Cusack, P. J. Smith and P. W .C. Barnard, Inorg. Chim. Acru, 1983,72,
217,
393. S. J. Blunden, P. A. Cusack, P. J. Smith and D. G. Gillies, Inorg. Chim. Acru, 1984,84,35.