Phosphorus-31 NMR Spectroscopy

Olaf Kühl

Phosphorus-31 NMR
Spectroscopy

A Concise Introduction for the Synthetic

Organic and Organometallic Chemist

123
Dr. Olaf Kühl
Universität Greifswald
Institut für Chemie und
Biochemie
Soldtmannstr. 23
17489 Greifswald
Germany
Email, personal: [email protected]

ISBN: 978-3-540-79117-1 e-ISBN: 978-3-540-79118-8

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Preface

Nuclear Magnetic Resonance is a powerful tool, especially for the identification of

hitherto unknown organic compounds. 1H- and 13C-NMR spectroscopy is known
and applied by virtually every synthetically working Organic Chemist. Conse-
quently, the factors governing the differences in chemical shift values, based on
chemical environment, bonding, temperature, solvent, pH, etc., are well understood,
and specialty methods developed for almost every conceivable structural challenge.
Proton and carbon NMR spectroscopy is part of most bachelors degree courses,
with advanced methods integrated into masters degree and other graduate courses.
In view of this universal knowledge about proton and carbon NMR spectros-
copy within the chemical community, it is remarkable that heteronuclear NMR is
still looked upon as something of a curiosity. Admittedly, most organic compounds
contain only nitrogen, oxygen, and sulfur atoms, as well as the obligatory hydrogen
and carbon atoms, elements that have an unfavourable isotope distribution when it
comes to NMR spectroscopy. Each of these three elements has a dominant isotope:
14
N (99.63% natural abundance), 16O (99.76%), and 32S (95.02%), with 16O, 32S, and
34
S (4.21%) NMR silent. 14N has a nuclear moment I = 1 and a sizeable quadrupolar
moment that makes the NMR signals usually very broad and difficult to analyse.
There are quite a few less common heteronuclei, particularly in Elementorganic
Chemistry, with highly important applications in catalysis, CˆC and CˆN bond
forming reactions, Medicinal Chemistry, Pharmacy, Green Chemistry and natural
product synthesis, to name a few, that would make studying their NMR spectros-
copy highly beneficial to that part of the chemical community that occupies itself
with the research, production, and distribution of these chemicals.
In particular, 31P (100%), 19F (100%), 11B (80.42%), and, to a lesser extent,
27
Al (100%), 29Si (4.70%), and 195Pt (33.8%) are arguably the most important het-
eronuclei in NMR spectroscopy. There are excellent books and reviews available
that deal with some regions of the chemical shift range of these heteronuclei,
together with a plethora of highly theoretical books and reviews on all aspects
of instrumentation, algorithms, Hamiltonians, pulse sequences, etc., which may
be very beneficial to the technician or the NMR specialist, but which are almost
meaningless to the Synthetic Chemist. The Synthetic Chemist is interested in
the identification of a compound, and thus uses the chemical shifts as a means
to establish a link to the heteronucleus contained in the compound, and needs a

v
vi Preface

means of identifying a chemical shift value that bears the structural aspects of
his/her proposed compound.
Heteronuclear NMR is highly useful in this context, since a given compound
normally contains only very few atoms of this nucleus, making the spectrum rela-
tively simple, especially when compared to carbon or proton NMR.
Simplicity is needed in explaining the very complex field of phosphorus NMR to
the non-specialist, and the Synthetic Chemist in particular. Simplicity is also the main
shortcoming of this book; complex explanations are sometimes deliberately and nec-
essarily oversimplified to keep the book in perspective and the intended reader in sight.
I am far from apologetic in this regard, since I believe that it is better to teach 99 stu-
dents to be right most of the time than just one to be completely right all of the time.
It is the primary aim of this book to enable the reader to identify the main factors
governing the phosphorus chemical shift values in the 31P-NMR spectrum, and to
make an educated guess as to where the phosphorus resonance(s) of a given target
compound can be expected. It is not within the scope of this book to enable one to
predict a phosphorus chemical shift precisely, or even within a reasonable margin of
error, with a few notable exceptions.
Whereas proton and carbon NMR spectroscopy is largely governed by σ-bonding
contributions or well-defined p -bonded units, the influence of p -bonding interac-
tions (hyperconjugation, negative hyperconjugation, and p -donor bonds) on the
phosphorus chemical shifts is much more frequent and larger in magnitude. There
are frequently no simple empirical formulae to describe the chemical environment
of phosphorus atoms, making a quantitative calculation very complex and impracti-
cal. In fact, most theoretical computations of phosphorus chemical shifts take days,
if not weeks, and plenty of financial and instrumental resources to produce the same
(or worse) results as the educated guess of a seasoned researcher in the field.
The further intent of this book is to assist the reader in determining important
issues, such as bond order, p -bonding contributions from substituents, the existence
or non-existence of metallacycles, etc.; in short, to make structural assignments
without the aid of X-ray crystal structure determinations or theoretical chemists, and
to explain structural differences in solution and the solid state where appropriate.
I regret that the book requires a good knowledge of organometallic chemistry for
those chapters dealing with phosphorus ligands and substituents bonded to metal
atoms. Those whose research takes them into the realm of metal coordinated phos-
phorus compounds undoubtedly already possess this knowledge. For those who
read on out of curiosity, my best advice to them is to peruse one of the many excel-
lent textbooks available in that field.
Acknowledgments

I thank the University of Alabama for a Visiting Professorship

I especially thank Dr. Joseph Thrasher, former Head of the Chemistry Depart-
ment, and Dr. Anthony J. Arduengo III., Saxon Professor of Chemistry, who worked
together to appoint me to teach “Spectroscopic Methods in Organic Chemistry”, the
course that gave birth to this book.
My gratitude to the students who contributed their motivation, abilities, and valu-
able comments to the making of this book:

Aymara Albury
Dionicio Martinez Solario
Amanda Joy Mueller
Jane Holly Poplin
Jason Runyon
Craig Wilson

I want to thank Prof. Masaaki Yoshifuji and Dr. Christian Schiel for their support
and encouragement, and Professors Pierre Braunstein (Université Louis Pascal,
Strasbourg, France) and Masaaki Yoshifuji (Tohilku University, Sendai, Japan;
University of Alabama) for their valuable comments on this manuscript.
I am indebted to Prof. Dietrich Gudat (Universität Stuttgart, Germany) for taking
the time to give me solid advice on the manuscript from a NMR expert’s perspec-
tive. The book would be much poorer without him, although I could not incorporate
all his suggestions in deference to my less specialised readership.

Greifswald, June 2008 Olaf Kühl

vii
Contents

1 Short Review of NMR Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

1.1 Origin of the Spectrum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Coupling to other Nuclei . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

2 The Range of Chemical Shifts, Coupling Constants,

and What Influences Each . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.1 Chemical Shift Values . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.2 Coupling Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.1 Coupling to Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.2.2 Coupling to Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.2.3 Coupling to Phosphorus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.2.4 Coupling to Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3 Oxidation State from P(−III) over P(0) to P(+V) . . . . . . . . . . . . . . . . . . . . . . . . 25
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

4 l5-Phosphanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35

5 l3-Phosphanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
5.1 Phosphorus Element Single Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
Box Story: Electronic and Steric Properties
of Phosphanes and Phosphites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
5.2 Phosphorus Carbon Multiple Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
5.3 Phosphorus Phosphorus Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
5.3.1 Diphosphanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
5.3.2 Diphosphenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68

ix
x Contents

6 Main Group Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71

6.1 As Lewis Base . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
6.2 As Lewis Acid P(I), P(III), and P(V) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81

7 Transition Metal Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83

7.1 Phosphanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
7.2 Chelate Phosphanes (Influence of Ring Size) . . . . . . . . . . . . . . . . . . . . . . . . . 87
7.3 Phosphides (Terminal and Bridging) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
7.4 Phosphinidines (Terminal and Bridging) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
7.5 Phosphaacetylene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
7.6 Agostic MˆPˆH Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
7.7 Naked Phosphorus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
Box Story: Isolobal Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126

Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
List of Abbreviations

Ad adamantyl
Bui iso-butyl
Bun n-butyl
But tert-butyl
Bz benzyl
C11 (4) from graph theory: a repetitive chain sequence consisting of four atoms,
one of which is a hydrogen donor and another is a hydrogen acceptor
Cp cyclopentadienyl
CpR substituted cyclopentadienide
Cp* pentamethyl cyclopentadienide
Cp° tetramethylethyl cyclopentadienide
Cy cyclohexyl
d doublet
d chemical shift
dC carbon chemical shift
Δcoord coordination chemical shift
Δd difference between two chemical shifts
ΔI quantum transition of the nuclear spin
dp phosphorus chemical shift
dppe bis-diphenylphosphinoethane
dppm bis-diphenylphosphinomethane
dppp bis-diphenylphosphinopropane
ΔR ring chemical shift
Ear aryl effect parameter (QALE parameter)
Et ethyl
fac fac (Δ-shaped) substitution pattern on octahedron
FT fourier transform
g magnetogyric ratio
gem geminal
h hapticity: number of atoms a ligand uses to bond to the same metal atom
HOMO highest occupied molecular orbital
I nuclear spin
I-effect inductive effect

xi
xii List of Abbreviations

k number of atoms a ligand uses to coordinate to metal atoms

L ligand, s -donor
l3 trivalent (phosphorus)
l5 pentavalent (phosphorus)
LUMO lowest unoccupied molecular orbital
m magnetic moment
bridging atom or ligand
Me methyl
M-effect mesomeric effect
mer meridial (T-shaped) substitution pattern on octahedron
Mes mesityl, 2,4,6-trimethylphenyl
Mes* supermesityl, 2,4,6-tris-tert-butylphenyl, also known as Smes
n frequency
OTf triflate CF3SO3−
PALP phosphorus atom lone pair
Ph phenyl
Pri iso-propyl
Prn n-propyl
p-Tol para-tolyl
P4 white phosphorus, a P4-tetrahedron
q quartet
QALE quantitative analysis of ligand effects
pp p-acidity (QALE parameter)
s singlet
sc shift parameter
∑ mathematical sign “sum of”
Smes supermesityl, 2,4,6-tri-tert-butylphenyl; also known as Mes*
t triplet
tbp trigonal bipyramidal
thf tetrahydrofuran
Θ dihedral angle (coupling)
Tolman’s cone angle (QALE parameter)
Tol tolyl
Tp tris-pyrazolatoborate
triphos tris-diphenylphosphino-tert-butane
VE valence electrons
VSEPR valence shell electron pair repulsion
VT variable temperature
cd s-donor capacity (QALE parameter)
*
asymmetric atom
chiral centre
Conventions

Stereochemistry

We will use the convention of Organic Chemistry to depict the stereochemistry

around a given atom. That means that the central atom and all other atoms con-
nected to it by a straight solid line are in the plane of the paper, an atom connected
by a solid wedge protrudes out of the plane (is situated in front of the paper) and
an atom connected to the central atom by a dotted line reclines behind the plane (is
situated behind the paper). This is illustrated in the following figures:
We will normally use the view on the left hand side for square planar (octahedral)
and tetrahedral geometries around the optically active atom. The second view for a
tetrahedral geometry shows the numbering scheme according to the Cahn, Ingold,
Prelog priority rules; whereas the third view shows that a tetrahedron consists of
two pairs of substituents that are in planes perpendicular to each other.

square planar

4 1
4
4
3 2
1 3
2 1 3
2

tetrahedral

xiii
xiv Conventions

NMR Standard

Phosphorus chemical shift values are given in ppm with 85 % H3PO4 as external standard
(unless otherwise stated), with positive numbers indicating a downfield shift.

Downfield Chemical Shift

A downfield chemical shift is characterized by a deshielding of the nucleus, and thus

an increase of the chemical shift value (toward the left of the spectrum).

Upfield Chemical Shift

An upfield chemical shift is characterized by a shielding of the nucleus, and thus a

decrease of the chemical shift value (toward the right of the spectrum).
Chapter 1
Short Review of NMR Theory

This book does not intend to explain NMR spectroscopy in full. It does not even
intend to explain enough theory to enable the reader to understand 31P-NMR spec-
troscopy without prior knowledge of 1H- or 13C-NMR spectroscopy. There are
many books that give a detailed explanation of 1H- and 13C-NMR spectroscopy.
It is expected that the reader of this book is familiar with these nuclei in an NMR
spectroscopic sense. However, a brief reminder of the basic concepts of NMR spec-
troscopy is given in this chapter as a way of introduction.

1.1 Origin of the Spectrum

An atomic nucleus contains protons, and, with the exception of 1H, neutrons. Each
proton and each neutron has an individual nuclear spin. The overall nuclear spin I of the
nucleus is determined by vector addition of the individual proton and neutron spins.
Note: Proton spins can only be canceled by proton spins and neutron spins can only
be canceled by neutron spins.
A quick estimate as to the nuclear spin being integer, half integer, or zero can be
made from the number of protons (atomic number) and neutrons (atomic mass – atomic
number) contained in that nucleus. A summary is given in Table 1.1.
A nucleus with a spin I = 0 has no NMR spectrum, it is NMR silent, and does not
couple to other nuclei. Important examples are 12C, 16O, and 32S. We are all familiar
with the consequences from 13C-NMR. Here the predominant isotope is 12C, an
NMR silent nucleus. The NMR active nucleus 13C has a natural abundance of only
1.1%. Coupling to 1H is observed and usually deactivated by broadband decoupling.
Coupling to carbon is not observed, except in the case of 13C enrichment, due to
probability constraints.
Note: Coupling to phosphorus – and other NMR active heteronuclei – is observed
in 13C-NMR spectroscopy.
Nuclei with I = 1/2 are called dipolar nuclei. They appear to be spherical, with a
uniform charge distribution over the entire surface. Since the nucleus appears to be

O. Kühl, Phosphorus-31 NMR Spectroscopy, 1

© Springer-Verlag Berlin Heidelberg 2008
2 1 Short Review of NMR Theory

Table 1.1 A quick guide as to whether an isotope has zero, half-integer, or integer nuclear spin
I Atomic Mass Atomic Number Nuclei
1
Half-integer Odd Odd 1
H(½), 3115P(½)
13
Half-integer Odd Even 6
C(½), 7332Ge(9/2)
14
Integer Even Odd 7
N(1), 21H(1)
12
Zero Even Even 6
C(0), 168O(0), 3216S(0)

spherical, it disturbs a probing electromagnetic field independent of direction. The

result is a strong, sharp NMR signal. 31P is a dipolar nucleus.
Nuclei with I > 1/2 are called quadrupolar nuclei. They have a non-spherical
charge distribution, and thus give rise to non-spherical electric and magnetic fields.
They are said to have a quadruple moment. The consequences are major complica-
tions in their NMR spectra manifested as severe line broadening, shallow peaks, and
difficulties with phasing and integration.
It is fortunate that 31P is a dipolar nucleus. However, it is frequently bonded to
quadrupolar nuclei, such as 14N, 59Co, 63Cu, 65Cu, 105Pd, 193Ir, and 197Au. The magni-
tude of complications depends on factors such as natural abundance of the isotope,
quadruple moment, and the relative receptivity.
Note: Phosphorus atoms bonded to quadrupolar nuclei can experience severe line
broadening.
The standard NMR experiment for a dipolar nucleus like 31P involves subjecting
the probe to an external magnetic field with constant field strength B0 and variable
radiofrequency n. In such a field, the phosphorus nuclei can either align themselves
parallel or antiparallel to the external field. This can be represented as Nα or Nß (see
Fig. 1.1). The nuclear magnetic moment m is directly proportional to the spin I of
the nucleus.

m=g I h/2 p

The proportionality constant g is called the magnetogyric ratio and is specific to

every nucleus. The energy ΔE required for a transition between the two states Nα
and Nß is the transition energy

E Νβ , β (–½)

I=½ ΔE

Να, α (½)
Fig. 1.1 A graphical
description of the transition
energy for a 31P nucleus Field Strength B0
1.1 Origin of the Spectrum 3

ΔE = (h g / 2 p )

Note: Only single quantum transitions, ΔI = 1, are allowed in NMR spectroscopy.

As NMR data is usually expressed in terms of frequency, it is better to convert the
transition energy ΔE to the corresponding frequency ν using the relationship ΔE = hn.

n = (g / 2 p ) B0

We know from 13C and 1H-NMR that there is a constant ratio between the res-
onance frequency and the applied field strength. The latter is an unchangeable
parameter in modern NMR spectrometers.

n / B0 = g / 2 p

The proportionality constant is the magnetogyric ratio, which, for a given

nucleus, in our case 31P, is a constant ratio between the radiofrequency and the
applied magnetic field. Since the applied magnetic field is constant for a given
NMR spectrometer, we will need to change the radiofrequency n, the MHz, for
each nucleus that we wish to measure.
Note: NMR spectrometers are named after the frequency they use to measure 1H
spectra. The required frequency for another nucleus, X, can be calculated from the
magnetogyric ratio of that nucleus.

n X = g X . n H/ g H

Note: As the frequency of the NMR spectrometer is increased, the field strength of
the magnet has to be increased in equal proportion. That is the reason for the infra-
structural difficulties encountered with NMR spectrometers over 500 MHz.
From Table 1.2, it can be seen that the magnetogyric ratio for phosphorus is about
2.5 times smaller than that for hydrogen. The required radiofrequency is therefore
also about 2.5 times smaller than that of the spectrometer. For a 400 MHz NMR
spectrometer, that would calculate to approximately 161 MHz.
So far, we have discussed the nucleus in terms of a specific isotope; in our case,
31
P. NMR spectroscopy is only useful to us because there is a difference between
phosphorus atoms in different local environments. Each phosphorus atom in its
own local environment is assigned its own chemical shift value, d P, measured in
ppm. We know from 13C- and 1H-NMR that the origin of the chemical shift lies
in the influence (shielding and deshielding) that the neighbouring atoms assert on
the phosphorus atom. Mathematically, we can describe this phenomenon by the
following equation:

neff = (g / 2 p) B0 (1−s )
 4

Table 1.2 The magnetogyric ratio and NMR frequencies of common nuclei
Nucleus Natural Magnetic Magnetogyric NMR frequency Standard Relative Relative
Abundance Moment Ratio Ξ [MHz] Receptivity DP Receptivity DC
[%] m [μN] g [107 rad T−1s−1]
1
H 99.985 4.83724 26.7519 100.000000 TMS 1.00 5.67 × 103
13
C 1.108 1.2166 6.7283 25.145004 TMS 1.76 × 10−4 1.00
15
N 0.37 −0.4903 −2.712 10.136783 MeNO2, [NO3]− 3.85 × 10−6 2.19 × 10−2
19
F 100 4.5532 25.181 94.094003 CCl3F 0.834 4.73 × 103
29
Si 4.70 −0.96174 −5.3188 19.867184 TMS 3.69 × 10−4 2.10
31
P 100 1.9602 10.841 40.480737 85% H3PO4 0.0665 3.77 × 102
1 Short Review of NMR Theory
1.2 Coupling to other Nuclei 5

The factor (1−s ) converts the general resonance condition for the nucleus 31P to
the specific resonance condition for the individual phosphorus atom in the actual
compound that we want to measure. The parameter s carries all of the influences
that our individual phosphorus atom is subject to. These are normally limited to
diamagnetic factors, such as electronegativity of substituents, and diamagnetic
anisotropy due to participation in double bonds or shielding cones of adjacent
functional groups.
Note: We will see that π-bonding has a very large influence on the chemical shift
values for phosphorus atoms in 31P-NMR spectroscopy.

1.2 Coupling to other Nuclei

31
P couples to any other nucleus with a nuclear spin I > 0. Apart from 1H and 13C (the
latter is only observable in carbon NMR spectra), 31P nuclei couple to themselves
(PˆP coupling), fluorine (19F), boron (10B and 11B), and a variety of metals, espe-
cially transition metals.
Most transition metals have a rather low natural abundance of the NMR-active
isotope. The appearance of the 31P-NMR spectrum is therefore that of a strong sin-
glet flanked by satellite peaks of the respective multiplicity (see Fig. 1.2).
Note: If the multiplicity is odd, then the strong singlet in the centre coincides with the
central line of the multiplet. Thus, the central line of the multiplet is much enlarged.
Note: If the metal has more than one NMR active isotope, more than one satellite
multiplet will be observed.
Coupling to 1H can be deactivated using proton broadband decoupling tech-
niques. The respective notations are 31P-NMR for the proton coupled spectrum, and
31
P-{1H}-NMR for the proton decoupled spectrum. This notation is analogous to
that used in 13C-NMR spectroscopy.

Fig. 1.2 A triplet

superimposed on a singlet
(looks like a doublet satellite)
6 1 Short Review of NMR Theory

Bibliography

Grim S O, Mitchell J D, Inorg Chem 16 (1977) 1770.

Harris R K, Mann B E, NMR and the Periodic Table, Academic Press 1978.
Kemp W, NMR in Chemistry, A Multinuclear Introduction, McMillan, 1986.
Nelson J H, Nuclear Magnetic Resonance Spectroscopy, Prentice Hall, Upper Saddle River, NJ
(USA) 2003.
Pregosin P S, Transition Metal Nuclear Magnetic Resonance Studies in: Inorganic Chemistry Vol.
13, Elsevier, 1991.
Pregosin P S, Kunz R W, 31P and 13C NMR of Transition Metal Phosphane Complexes, Springer-
Verlag, Heidelberg, 1979.
Silverstein R M, Webster F X, Kiemle D J, Spectrometric Identification of Organic Compounds,
7th Edition, John Wiley & Sons, Inc, New York, 2005.
Yadav L D S, Organic Spectroscopy, Kluiwer Academic Publishers, Dordrecht (NL) 2005.
Chapter 2
The Range of Chemical Shifts, Coupling
Constants, and What Influences Each

For over a century, since Lewis introduced his octet rule, chemists have been
accustomed to seeing the world of molecules through the glasses of two electron
two center bonds, commonly represented by a straight line between two atoms.
This image, developed into the valence bond VB-theory, is so powerful that it
was frequently and craftily adopted to accommodate every increase of insight
into the bonding between atoms in molecules achieved by progress in theoretical
chemistry methods, or in rival concepts such as the molecular orbital theory. We
now know of two electron three center bonds, four electron three center bonds,
one electron bonds, and many more, and we have a VB representation for each.
We have also developed a rich canon of names to describe our rapidly changing
perception of bonding in molecules, among which the terms “hyperconjugation”,
“negative (anionic) hyperconjugation”, “Heitler-London (HL) Increased-Valence-
Structures,” and “p -Donor Bonds” are those that concern us. We use them to explain
upfield and downfield chemical shifts in the 31P-NMR spectra of compounds that we
could not explain by “normal” s -bonds alone.
The common characteristic behind all of the above terms is the occupation of
previously empty orbitals with p -symmetry by electrons otherwise occupying
orbitals with s -symmetry. The term “p -bonding interaction,” frequently used in
this book, denotes a situation in which an (antibonding) orbital of p -symmetry
receives electron density from phosphorus or a neighbouring atom, thus significantly
influencing the phosphorus chemical shift. Nothing is implied as to the actual origin
of this electron density. It suffices for the main purpose of this book, which is to
predict the approximate region of the phosphorus resonances of a compound to
aid the synthetic chemist in identifying (new) compounds and describing their
31
P-NMR spectra.
However, we do need a basic understanding of the principal causes for these
p -bonding interactions. To this effect, brief and simple descriptions in lieu of
a detailed explanation are given for three main terms found in the literature.
p -Donor Bond The ability of a substituent to use a fully occupied p-orbital to
interact with the p -orbital of a P¨X bond or an empty p-orbital of phosphorus.
These p -donor bonds require coplanarity of the participating groups in order to
effectively form the four electron three center bond.

O. Kühl, Phosphorus-31 NMR Spectroscopy, 7

© Springer-Verlag Berlin Heidelberg 2008
8 2 Range of Chemical Shifts, Coupling Constants, and What Influences Each

P P P

Mes* Cl Mes* Cl Mes* Cl

Fig. 2.1 Graphical representation of p-donor bonding in a color-phosphaalkene

The case, of course, becomes clearer when the phosphorus atom carries a positive
charge. Then the familiar situation of a full p-orbital on the X atom interacting with
an empty p-orbital on P to form P¨X+ arises.
Hyperconjugation Hyperconjugation originally describes the conjugation
of a s -bond with a double or triple bond. It is, therefore the interaction of the
p -symmetric orbitals of this single bond with a p-orbital of this double or triple
bond. More generally, it is a s ⇒ p * or n ⇒ p * interaction. In Fig. 2.2, we see an
interaction that results in a partial double bond character of the P-N bond.
The main difference between hyperconjugation and p -donor bonds, in practical
terms, is that hyperconjugation does not require coplanarity, but is effective for all
angles ≠ 90°. The magnitude of the effect is angle dependent.
Negative Hyperconjugation Negative hyperconjugation, also known as anionic
hyperconjugation, is essentially the complementary interaction to hyperconjugation,
with opposite electron flow. Consequently, we have to denote it p ⇒ s * or p ⇒ n.
The complex bonding situation in phosphaneoxides (-sulfides and -imines) can
be simplified to a description of negative hyperconjugation, where the double bond
resolves into a lone pair (on E) and a positive charge, located on phosphorus. Not
surprisingly, with reference to the double bond rule, the third row element sulfur
prefers charge separation, whereas the second row elements oxygen and nitrogen
preserve a larger double bond character.

N P

Fig. 2.2 Hyperconjugation

in an N-P + cation

E E

P P
R R R R
R R
Fig. 2.3 The bonding in
phosphaneoxides, -sulphides,
and -imines E = NR, O, S