2

ATOMIC AND MOLECULAR

PROPERTIES OF SILICON

2.1. ATOMIC PROPERTIES

2.11. General
Silicon is found in nature bound to oxygen as silica and silicates. Approximately
28% of the earth’s crust is comprised of silicon, second in elemental abundance
only to oxygen (49.5%).’ The natural distribution of silicon isotopes is shown in
Table 2.1. Only the 29Si isotope with spin and, regrettably, low abundance, is
active in the NMR experiment. As we saw in Chapter 1, this is a very powerful
technique for the structural characterization of silicon-containing species.
Intuitively, the proximity between silicon and carbon on the periodic table
suggests their chemistries should be very similar. This is, in fact, only true with
silanes bearing four carbon substituents.The enhanced reactivity of silanes when
compared to analogous carbon compounds, particularly to nucleophilic sub-
stitution, is generally related to three characteristics of silicon: larger size (Table
2.2)’ lower electronegativity (Table 2.3), and the availability of low-energy
orbitals (in earlier literature, d orbitals, more recently other orbitals such as (T*
orbitals, three-center molecular orbitals, or ionic effects, see below).

2.1.2. Electronegativity
Silicon is often polarized in the opposite sense to carbon. With the exception of
bonds between silicon and very electropositive elements such as the alkali
metals, silicon is depleted of negative charge Sis+-Xs-. This difference is
exemplified by the two similar reactions shown in Scheme 2-1: whereas
the nucleophile (base) Me- attacks at H6+of the C-H bond, it is the Si6+ of the
Si-H bond that is attacked (note that in the absence of phenyl groups on silicon,
27
28 ATOMIC AND MOLECULAR PROPERTIES OF SILICON

Table 21. Natural Abundance of Silicon Isotopes

Spin quantum
Isotope Abundance2 number I
**Si 92.18% 0
29~i 4.7 1% 1I2
30~i 3.21% 0

Table 2.2. Comparison of Si and C Radii

Si C
1.06 A atomic radius3 0.66 A
1.17 A covalent radius4 0.77 A

other reaction pathways than that shown in Scheme 2-1B are followed; see
Chapter 3).5
A
8- 6+
Ph,C-H +
6- 6+
H,C-Li - Ph,C-Li 4- H,C-H

B
6+
Ph,Si-H
6-
+ 6- 8+
H,C-Li -
Scheme 2-1
Ph,Si-CH, + Li-H

The reactivity of a covalent bond, particularly under ionic conditions, can be

predicted by the differences in electronegativity of the two bonding atoms. This

Table 2.3. Electronegativityof the Atoms to Which Silicon Usually

Forms Bonds (Allred-Rochow values in Bold;' ab initio calculated
values in /ta//cs7)
~

H B C N 0 F
~ ~~ ~

2.20 2.01 2.50 3.07 3.50 4.10

2.79 1.84 2.35 3.16 3.52 4.0

A1 Si P S c1
1.47 1.74 2.06 2.44 2.83
1.40 1.64 2.11 2.52 2.84

Ge As Se Br
2.02 2.20 2.48 2.74
1.69 1.99 2.4 2.52
 ORBITAL INTERACTIONS OF SILICON: ATOMIC ORBITALS 29

is certainly true for silicon. The greatest bond polarization occurs with Si-0 and
Si-X (X =halogen, Table 2.3), bonds that are kinetically very reactive under
ionic conditions.

2.1.3. Covalent Bond Strengths

A comparison of Si-X and C-X bond strengths clearly shows another way in
which the two elements are different (Table 2.4). The bonds between silicon and
the halogens or oxygen are exceptionally strong-Si-F is one of the strongest
single bonds between any two elements on the periodic table. By contrast, the
bonds between silicon and N, Si, and H are much weaker. The trends are
somewhat reversed for carbon, where the C-H bond is unusually strong, and the
C-0 and C-halogen bonds are weaker than in the case of silicon. This has
important consequences in the relative reactivity of silanes, with respect to
carbon species, as will be discussed later (Chapters 12, 14-16).
It should be noted that the values presented in Table 2.4 are bond dissociation
+
energies for homolytic cleavage (R3Si-X + R3Si’ X’), a rather unusual type
of reaction for silicon, which generally undergoes ionic reactions (R3Si6+-
X6- .--t “R3Si f 9) +
X-).’ Therefore, one must use caution in using the values in
Table 2.4 to predict reactivity. For example, in spite of the very strong Si-F
bond, molecules containing these bonds are kinetically very reactive: F- can be
used as a catalyst for the cleavage of other Si-X bonds (silicon normally
participates in bimolecular reactions in which bond forming and breaking are
simultaneously taking place).’
The bond lengths provided in Table 2.4 are for tetracoordinate silicon species.
As silicon expands to 5- and 6-coordinate species, there is a corresponding
increase in bond lengths.”

2.2. ORBITAL INTERACTIONS OF SILICON ATOMIC ORBITALS

Silicon normally utilizes 3s and 3p orbitals for bonding. The vast majority of
naturally occumng or synthetic silicon compounds are tetrahedral (sp3
hybridi~ation~~). With four different substituents, the compounds are chiral:
Sommer made the first functional chiral silane [(menthyloxy)methyl-a-
naphthylphenylsilane] and used it extensively to investigate the reaction
mechanisms of silicon (Chapter 5).28Although much less usual than for carbon,
silicon can form double bonds. Such r-bonded species have been observed in the
gas phase (the first firm evidence for a triply bonded species, HC =Six, has also
a~peared).~’ In exceptional cases the doubly bonded species have been isolated
in crystalline form (Chapter 3).’6730
Silicon also has energetically accessible d orbitals. In earlier literature, these
were used to account for extracoordinate silicon compounds (penta- and
hexacoordinate; see Chapter 4). More recently, many authors refute the
importance of d orbitals in silicon bonding.31 These authors suggest that other
30 ATOMIC AND MOLECULAR PROPERTIES OF SILICON

Table 2.4. Approximate BondDissociationEnergies and Bond Lengths for Si-X and C-X

Bond energy Bond Bond energy Bond

(H mol- '1 lepgth H mol- leqgth
Bond Compound (kcal mol-') (A)" Bond (kcal mol-l)b (A)'
Si-C H3 Si-CH3 369 (88)' 1.87 C-C 334 (80) 1.53
H3Si-CMe3 376 (90)'
Si-H H3Si-H 378 (90)' 1.48" C-H 420 (100) 1.09
Me3Si-H 378 (90)'.
398 (95)"
C6H5H2Si-H 369 (88)'
C13Si-H 382 (91)"
F3Si- H 419 (100)'
H3SiHzSi-H 361 (86)'
(Me3Si)3Si-H 331 (79)d
Si-Si H3 Si-SM3 308 (74)' 2.34 C-C 334 (80) 1.53
Me3Si-SiMe3 332 (79)13
Si-0 Me3Si-OH 536 (128)' 1.63 C -0 340 (81)' 1.41
Me3Si-OMe 477 ( 1 14)'
Me3Si-OEt 484 (116)'
Me3Si-OSiMe3 549 (131) est.'
Si-S H3 Si-SSiH3 293 (70) est.' 2.14 C-S 313 (75)' 1.80
Me3Si-SC4H9 414 (99)b Me3C-SC4H9 297 (71)b
Si-N Me3Si-NMeH 401 (96)' 1.74 C-N 335 (80)' 1.47
Me3Si-N(SiMe3)z 434 (104) est.'
Si-F Me3Si-F 665 (159) est.' 1.6 C-F 452 (108)" 1.39
H3 Si- F 628 (150) est."
F3 Si-F 694 (166)b F3C-F 544 (130)b
Si-Cl Me3Si-Cl 472 (113)' 2.05 C-Cl 335 (80)" 1.78
H3 Si-Cl 451 (108)"
C13Si-Cl 449 (107)' C13C-CI 297 (71)b
Si-Br Me3Si-Br 402 (96)' 2.21 C-Br 268 (64)' 1.94
H3Si-Br 370 (88)'
C13Si-Br 368 (88)"
Si-I Me3Si-I 321 (77)' 2.44 c-I 213 (51)' 2.14
H3 Si-I 321 (77) est.'
C13Si-I 276 (66)"
s-Bond energy s-Bond energy
Si=Si MeszSi=SiMesze 105-126 2.1617 C=C 272 (65)"
(25-30) 14-"

Si=C 1.70"

OSiMe,

x siA
I
R = adamantyl 1.76"
Me.Si

'Tabulated by E. W. C01vin.'~
bBond strengths determined and tabulated by R. Walsh."
'Bond strengths determined and tabulated by R. Wal ~ h . 2~
Bond strengths determined by C. Chatgilialoglu?6
Mes = mesityl = 2,4,6-trimethylphenyl.
Table adapted from Ref. 23 with permission. Copyright E. W. Colvin.
 MOLECULAR PROPERTIES OF SILICON 31

orbitals, such as three-center molecular are important in the

bonding configurations of silicon, including extracoordination. The require-
ments for bonding in extracoordinate silicon include: electronegative ligands
(which typically occupy the axial positions in trigonal bipyramidal or octahedral
structures), longer bonds in the extracoordinate than in the tetrahedral system,
and a decreased electron density at silicon (however, see Chapter 4). The
experimental observations, for example, that in SiF5- the axial bonds are longer
and more polar than the e uatorial bonds, are accommodated by both the
hypervalent bonding ~ i c t u r ? ~and the use of d orbitals (3sp3d)?’ The author
will equivocate on this question and use both the traditional d orbital
nomenclature (Chart 2- 1) and the a*/three-center molecular orbital picture in
the following discussion. For a more detailed discussion of this point, the reader
is referred to reviews on the subject.34

1-
2-
ax
Bond angle I Bond angle 1 ..,q
eq,,,,
ax-Si-eq 900 eq-Si, l e q ax-si-eq 900 eq+eq
ax ax
eq-Si-eq 1200 ax eq-Si-eq 900
ax-Si-ax 1 8 8 ax-Si-ax 1800
trigonal bipyramid octahedron

Chart 2-1

2.3. MOLECULAR PROPERTIES OF SILICON

In organic chemistry, carbon skeletons are held together by covalent bonds.

Although the covalent bonding of tetraalkylsilanesis very similar to the alkanes,
some variations on the covalent bond theme are possible for halo-, amino-, and
alkoxysilanes. There is an ionic component to the bondin due to the very large
difference in electronegativity between the two elements!‘ Moreover, there can
be back-donation, with 7r symmetry, from the lone pair on the heteroatom to the
silicon atom.

2.3.1. Backbonding between Silicon and Heteroatoms:

d Orbitals versus Q* Orbitals
The exact nature of the bonding to heteroatoms in the case of silicon has proven a
rich area of research. Three different views have emerged, which are presented
below in chronological order: backbonding through d orbitals, through a *
orbitals and contributions from ionic structures.
In organometallic chemistry, back-donation generally occurs from the lone
pair on an adjacent heteroatom into an appropriately oriented d orbital on a metal
center.37 As noted above, a relatively contentious argument has raged in the
literature regarding this bonding picture for silicon. Earlier work, until about the
middle 1960s, generally assumed that these interactions involve d orbitals on
silicon (Chart z ~ A ) . ~NMR
* experiments, in particular, support the &orbital
32 ATOMIC AND MOLECULAR PROPERTIES OF SILICON

~ i c t u r e . ~More
* * ~ recent
~ work, articularly that based on ab initio calculations,
NMR:’ and other experiments? suggests that the significant participation (that
is, more than about 10%) of d orbitals in bonding interactions is precluded,
because their energies are generally too high. Other orbitals must, therefore, be
involved!’ Silicon has low-lying o* orbitals, by virtue of its low electro-
negativity, which are of the correct symmetry to participate in .Ir-type back-
bonding interactions (Chart 2-2B).43

A: Si dxyorbital, Si-X x-type bond B: Si-C CJ* bond, Si-X a-type bond
Chart 2-2

Back donation has been used to account for the following observations:

Increased acidity of silanols when compared to alcohols. The removal of

electron density from 0 makes the H more acidic (Chart 2-3). Although
older literature, from IR studies4 suggested that Ph3SiOH has a
pK, x 10, much more acidic than Ph3COH, the direct measurement of
the pK, in DMSO suggests increased acidity, but of a lower magnitude
( p k : Ph3SiOH 16.57; Ph3COH 16.97):’ The basicity of ethers follows
the order R3COCR3 > R3SiOCR3 > R3SiOSiR3:6

H
H
H
--+/
R,Si -0

d orbital picture a*orbital picture

Chart 2-3

(2) Low bending force constants around Si-0-Si and other heteroatom
bonds (linearity in the limit with Ph3SiOSiPh3).Bond lengths and angles
around silicon can be affected greatly by steric overcrowding and by the
nature of the central atom. Stress caused by sterically bulky silyl groups
can be relaxed by stretching the bond lengths andor increasing bond
angles. With carbon as a central atom (Si-C-Si), the bond angle is close
 MOLECULAR PROPERTIES OF SILICON 33

to tetrahedral (up to 123" in Me3SiCH2SiMe3). With a central

heteroatom, however, the an les are readily deformed even in the
absence of large bulky groups.F1The barrier to linearization of Si-0-Si
in dimethylsilicones, for instance, was found to be only 1.25 kJ mol-
(0.3 kcal mol- 1).47 This can be explained by donation of one of the lone
pairs on 0 into silicon orbitals to change the effective hybridization at 0
from sp3 towards sp (shown in the limit of sp hybridization, Chart 2-4;
see also the discussion on ionic character below) [Si-0-Si angle:
Ph3SiOSiPh3 180"," Me3SiOSiMe3 154", N O(Me2SiOSiMe2)0N
(D,) 145°48].

Chart 2-4

(3) Low barrier to pyramidal inversion with silyl ~ m i n e sThe

.~~intermediate
state between the two pyramidal forms or silazanes is stabilized by
orbital overlap between silicon and nitrogen. N(SiMe3)349 and
(PhSiH2)3N50are planar, as shown by electron diffraction techniques
and X-ray crystallography, respectively (Chart 2-5). Consistent with this
picture is the reduced gas-phase basicity of silazanes when compared
with the analogous amines (e.g., t-BuMe2SiNMe2 is less basic than
t-B~Me~cNMe~).~l
R'
~.> R2
R,Si -

..1...
R
via
RZ
R,Si -N ,..,.,,,,,,
\ R'
R2
d orbital picture
Chart 2-5

(4) Unexpectedly short bond lengths for Si-OR, Si-N, and Si-F." The
bond lengths are much shorter than the sum of covalent radii. Because of
suitable orbital size, effective orbital overlap with Si-0 and Si-F leads
to a bond that is stronger than a (T bond, in the range of the sum of a (T
bond + $ T bond (Chart 2-6).
34 ATOMIC AND MOLECULAR PROPERTIES OF SILICON

R’

d orbital picture a*orbital picture

Chart 2-6

It should, in principle, be relatively easy to discriminate between the two

modes of bonding. Backbonding to silicon d orbitals involves only bonding
interactions. The r-type interaction between the lone pair and the d orbital is
stabilizing and is rotationally degenerate. As the Si-X bond is rotated, there is
always an appropriately oriented d orbital that can participate in bonding
(Scheme 2-2). There is no countervailing, antibonding contribution.
By contrast, to the extent that Si-X backbonding occurs through o* orbitals,
the strength of such a bond will be rotationally dependent. A partial r bond can
only arise when the torsional angle between the o*orbital and the lone pair is 0”
(Scheme 2-3A). Rotation around the Si-X bond, by 90”, for example, leads to
loss of the stabilizing “-type interaction (Scheme 2-3B). The consequence
of populating the o*orbital with electron density from the lone pair, to create the
“-type Si-X interaction, is a weakening of the u bond!1

dXY dXZ

Si-C n-type bond Si-C n-type bond

Scheme 2-2

Si-C u bond A: Si-C u* bond, 6:Si-C u* bond,

Si-X n-type bond no Si-X x-type bond
Scheme 2-3
 MOLECULAR PROPERTIES OF SILICON 35

2.3.2. Bonding between Silicon and Heteroatoms: Ionic Factors

More recently, a much simpler view of bonding in silicon compounds has
arisen.52If one plots bond strength versus electronegativity,there is a very clear
correlation (Figure 2.1). Stronger bonds are formed with more electronegative
groups, it is proposed, because of the increase in contributions from ionic
structures Si6+-X6-. This would explain why Si-C and Si-S bond strengths are
similar: The electronegativities of S and C are comparable. Thus, in spite of
available lone pairs on sulfur for backbonding, none is observed. Such a view
can similarly account for the large bond angles and the low bending force
constants for Si-0-Si angles. Not all of the observations are explained by this
proposal, Section 2.3.1., (1) in particular. For instance, to the extent that the
oxygen in Si-0 is electron rich, it should be more basic, not less basic, than the
carbon analogue C-0.
It is clear from calculation and experiment that silicon shares electrons with
its bonding partners in a different manner than carbon. Experiments that support
all three pictures of bonding interaction exist. The purpose in outlining these
bonding arguments is to draw attention to the possibility of the n-type bonding
interaction. The exact nature of the orbital picture, for the purposes of this book,
is of less importance (a*orbitals are primarily used in the remainder of the
book).

700 -
* F
600 --

500 --
-
7

7
Y
z 400 --

s
-g
300 --

o 200 -- + Li

100 --

04 I
0 2 4 6
Allred-Rochow Hectronegativity of X
Figure 2.1. Plot of calculated Si-X bond strength in H3Si-XH, versus the Allred-Rochow
electronegativity of atom X. Adapted with permission from Ref. 36. Copyright 1986 American
Chemical Society.
36 ATOMIC AND MOLECULAR PROPERTIES OF SILICON

2.4. REFERENCES

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38 ATOMIC AND MOLECULAR PROPERTIES OF SILICON

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