SILICON-BASED REACTIVE

INTERMEDIATES

As we saw in Chapter 2, the properties of silicon in organosilanes are quite

different from those of carbon in organic compounds. However, the two
elements share many of the same bonding configurations (Chart 3-1),' reaction
mechanisms, and reactive intermediates (Chart 3-2).2,3 The disparities in
reactivity between the two elements lie in the relative stability of those different
bonding configurations and reactive intermediate^.^ For instance, silicon
participates much better in extracoordinate bonding (>4) than carbon. By
contrast, carbon forms more stable T bonds than silicon. In fact, multiple bonds
to silicon were thought, prior to 1967: not to exist or to exist only fleetingly as
reactive intermediates.6

rare
or unknown
-
-

rare or unknown common

Until the watershed year of 1981, much of the mechanistic understanding of

organosilicon chemistry arose from careful kinetic and trapping studies. A
variety of reactive intermediates, many related to the better-known organic
analogues (Chart 3-2), were proposed as a result of these investigations. At the
39
40 SILICON-BASED REACTIVE INTERMEDIATES

&C: R,C+ R3Ce R,C -

r 1

X = C, 0, N, Si, P,etc.
Chart 3 - 2 Reactive intermediates of silicon and carbon

XIVth Organosilicon Symposium in 1981, two seminal papers were presented

that, for the first time, indisputably demonstrated that two of the proposed
reactive intermediates existed: They had been isolated. These were the papers of
Brook et d7 and West and co-workers’ describing the first X-ray crystal
structures of a silene (Si=C) and disilene (Si=Si), respectively. In both cases, the
kinetic stability of the silicon double bonds resulted from steric encumbrance.
Since that time, stable versions of many other silicon-based reactive
intermediates have been isolated, most utilizing the same principle. These
include silylenes (R2Si:), silanimines (R2Si=NR‘), silanethiones (R2Si=S), and
related heavier element analogues.
In this chapter, the properties of some silicon-based reactive intermediates,
including ionic and 7r bonded systems, will be outlined. Note that although the
terms “silyl cation,” “radical,” and “anion” are found frequently in
mechanistic discussions of silicon, the nomenclature more frequently reflects
the reactive behavior of the compounds rather than absolute structures. Thus
“silicon cations” may be associated with electron-deficient silicon atoms (e.g.,
R3SiOS02CF3, R3SiOC103, R3SiI), “silicon radicals” are often alluded to
because of the reaction conditions used (e.g., peroxides), and the term “silyl
anion” is used with metallic silicon species [e.g., (R3Si)2CuLi]that have not
been characterized as free ions. Only in exceptional cases are the structures of
such reactive intermediates rigorously proven. The discussion that follows relies
on reports of both inferred and stable, isolated structures of the “reactive inter-
mediates.” It will be extended to a more general analysis of mechanistic and
synthetic organosilicon chemistry in Chapter 5 (nucleophilic substitution),
Chapters 6-1 1 (formation and cleavage of Si-X bonds, X # C), and Chapters
12-16 (formation and cleavage of Si-C bonds).

3.1. SILYLENES @&I:)

Silylenes:.’o the silicon analogues of carbenes, are highly reactive divalent

species. The trend down the Group 14 column of the periodic table is increased
stabilization for the divalent state. Thus silylenes are more stabilized, relative to
silyl radicals, than is the case between carbenes and carbon-centered radicals.’ ’
Silylenes are generated as sin lets, for H2Si: M 79 kJ mol-’ (19 kcal mol- ’)
below the triplet (Chart 3-3),’27’3whereas the parent carbene H2C: is a tri~1et.l~
 SILYLENES (R2SI:) 41

This difference between carbon and silicon has been ascribed to different
HOMO-LUMO gaps in the divalent species of the two elements: The HOMO-
LUMO gap is much larger in the case of silicon (218 kJ mol- 52 kcal mol- ') ',
',
than carbon (13 1kJ mol- 31 kcal mol- ').3 For substituted silylenes, as with
carbenes, calculations show that the singlet and triplet states are differently
affected by the nature of the s~bstituent,'~
7~ donors (e.g., heteroatoms with lone
pairs, 0, N, etc.) stabilize the singlet state in particular. This suggests that
backbonding, of the type already discussed in Chapter 2, may be important.
Walsh and co-workers have estimated the divalent stabilization energy of
silylenes, as shown in Table 3.1 [DSSE (R2Si:) = D(R3Si-R)-D(R2Si-R), where
R is the substituent on the ~ilylene].'~*'~

Silylene Triplet (diradical) Singlet (cation, anion) rc-Stabilized Singlet

Chart 3-3: Behavior of divalent silicon species

The electronic spectra of saturated and unsaturated silylenes have been

measured in argon and hydrocarbon matrices. Me2Si: absorbs at 453nm,
MesMeSi: at 495, and Me3SiC=C(Me)Si: at 473 nm.18-21The corresponding
disilenes (silylene dimers) absorb at much lower wavelengths [e.g., Me3SiC=
C(Me)Si=Si(Me)C=CSiMe3 at 410nm, see the discussion on disilenes].

3.1.1. Preparation of Silylenes

The most common route for silylene generation involves Si-Si bond cleavage.
This takes advantage of the low energy of the Si-Si bond both to thermolysis
and photolysis.22In special cases, the photolysis of disilanes leads to ~ i l y l e n e s ~ ~
(e.g., flash photolysis of C13SiSiC13--+ C12Si:).2'24A more general route to
silylenes is the photolysis of l i n e d 5 or cyclic26trisilanes, tetra~ilanes;~oligo-,
and olysilanes (Eiq. 3.1;8 see also the discussion on polysilanes in Chapter
11).1',20729.30 For instance, photolysis of the silyltrisilane 3-1 leads first to the

Table 31. Divalent StabilizaHonEnergy (DSSE) for Silylenes

Molecule DSSE kJ mol-' (kcal rnol-')

H2Si: 81 (19)
MeHSi: 101 (24)
Me2Si: 118 (28)
H3SiHSi: 54 (13)
Adapted with permission from Ref. 16. Copyright John Wiley
and Sons.
42 SILICON-BASED REACTIVE INTERMEDIATES

alkoxysilylsilylene, which can be trapped by butadiene to give the cyclic silane

3-2(note that silenes and radicals3' may also be formed). Iteration of this process
leads to the spiro compound 3-3 (Scheme 3-1).32,33The extrusion of silylenes
from linear or cyclic oligosilanes occurs in a concerted manner.34The reaction
can be highly stereoselective, as shown in the ring contraction of 3-4 (Eq. 3.2).35
The formal extrusion of silylenes from trisilanes may also be mediated by
Pd(Ph3)4and other transition metal catalyst^.^^

Me,Si(SiMes),SiMe, hv * Me3SiSiMe, + tSiMes, (34

3-1 3-2
Scheme 3-1

Silylenes may be generated from a variety of cyclic precursors. One route

involves ring fragmentation with concomitant (re)generation of an aromatic
system, which compensates energetically for the cost of forming the silylene.
The use of rearomatization chemistry, as will also be seen with disilenes and
silenes, is attractive because the synthesis and characterization of the starting
material is reasonably straightforward (Scheme 3-2).37
Me, ,Me Ph

Ph -solution Ph
+ :SiMe,
CH OH
&H,
y

*0
SiMe,
3

Ph
Scheme 3-2

The thermolysis of silacyclopropanes (siliranes) leads to the formation of

silylenes (Scheme 3-3A; siliranes are much more reactive than the correspond-
ing silacyclobutanes). The first synthesis of a silirane was reported by Lambert
and Se~ferth.~* Siliranes are more enerally prepared by traditional routes such
as that shown in Scheme 3-3A39*45or via the reaction of cyclotrisilanes with
dienes and olefins, in which case the silylenes generated are trapped by the C=C
7r system. Another method involves the preparation of siliranes from other
 SILYLENES (R2SI:) 43

siliranes, by swapping alkenes?l This route was used to prepare the more highly
strained silirenes (1-silacycloprop-2-enes, Scheme 3-3B4') such as 3-542;the
example shown is stable to di~tillation!~~ Silirenes will, however, also
thermolyze to give silylenes.4 Siliranes generally react highly exothermically
with 02,H20, S8, HCI, and rapidly, even at -70°C, with Siliranes also
undergo insertion reactions with olefins to form silacyclopentanes, a reaction
that does not involve silylenes (Scheme 3-3C).46

A Me,Si
r Br
LBrTHF
Mg
- Me,Si
3 108OC
- -
- + :SiMe,

Scheme 3-3

The relief of strain in small rings also provides sufficient driving force to
prepare silylenes from silacyclobutanes, silacyclobutenes,'0~47and cyclotrisi-
+
lanes?8 The former compounds fragment via a retro [2 21-cycloaddition to
produce silenes and alkene~.~' A silene bearing an Si-H group can rearrange to
the silylene (see below, Scheme 3-4).50 The isomerization of silenes 3-6 to
silylenes 3-7 (and vice versa) has been examined for a number of systems (see
Chapter 15).51At 471"C, for instance, the AGZ = 178kJmol-' (43 kcal mol-')
for the rearrangement in Scheme 3-4A, as shown by trapping studies with
+
butadiene: Both silene ([2 41-cycloaddition-+ 3-8) and dimethylsilylene-
+
derived products (3-9 3-10) are observed (Scheme 3-4).s2*53The energ
difference between the silylene 3-7 and silene 3-6 is rather small in this case.2

3-8 3-9 3-10

Scheme 3-4
44 SILICON-BASED REACTIVE INTERMEDIATES

The reduction of chlorosilanes by alkali metals leads to the formation of

oligo- and polysilanes (Scheme 3-5,see Chapter 1 Monohalosilanes are
converted into d i ~ i l a n e s .This
~ ~ Wurtz-Fittig-like condensation probably
proceeds via both silyl anions and silylenes. In the absence of steric blocking
groups, the intermediate silylenes undergo oligomerization or polymerization.
For this reason, polysilanes are sometimes called polysilylenes.
(R,Si), (R2Si)6
R=tBu, CPr
7445% NalK
NaNp
THF
70% 75%
R=Me
LilNp NalK
(R2W3 4

lo%, R = Mes A D R=Me

90%

Np=Naphthalenide
Scheme 3-5

3.7.7.7. Stable Si/y/enes A new era in the study of silylenes began with the
isolation of the first stable Si" species by Jutzi and c o - w o r k e r ~ Using
.~~~~~
similar conditions to those described above, but with the very bulky Cp' groups
(Me5C5) as the organic ligands, the reduction of Cp*zSiClz with sodium
naphthalenide (or other alkali metals) led to the silylene Cp*zSi:(silicocene or
silacene, in analogy with ferrocene). The compounds could be isolated and
characterized by X-ray crystallography (Eq. 3.3). Initially, there was some
controversy about the electronic structure of this species. In the crystal, both
linear (3-11) and bent forms are observed. It was thought that both singlet and
triplet species might be present. Subsequently, calculations and the consideration
of crystal packing forces led to the conclusion that the bent form could also be
the singlet form of the silylene.

+ M - + Si : (3.3)

4 3-1 1

More recently, a remarkable class of stable silylenes 3-12 has been

reported.60361The flanking t-butyl groups provide some kinetic stabilization to
the silylene due to steric effects. However, electronic factors arising from the
pseudoaromaticity of the compounds are primarily responsible for the stability
of these systems. Quantum mechanical calculations suggest the unsaturated,
 SILYLENES (RzSI:) 45

+
aromatic [2 x lone pair (on N) alkene = 6e] silylene 3-12 is 58 kJ mol-
(14 kcal mol-‘) more stable than the saturated analogue 3-13 (Chart 3-4).60*62
Silylenes 3-12 and 3-13 are much more stable than silacenes 3-11 noted above,
displaying no reaction with typical silylene traps (HSiEt3)nor polar compounds
such as THF, pyridine, PMe3, and NEt3. They can, however, be converted into
silanimines (see below),63 undergo lP-additions with arylimines,64and form
metal silene complexes with nickel.65The analogous silylene 3-14 undergoes a
series of interesting reactions with ketones.66

A-
3-12 3-13 3-14

Chari3-4

3.1.2. Reactions of Silylenes

Silylenes typically participate in two types of reactions: addition to 7r systems, as
shown above, and insertion into o bonds. Silylenes usually react as electrophiles,
formally undergoing initial attack by a nucleophile into the empty 3p orbital
(recall, silylenes are ground-state singlets). In the absence of other reagents,
dimerization (Scheme 3-6A) readily occurs to form the disilene (see below) if
the concentration of silylenes is sufficiently high.67 Unless bulky groups are
present on silicon, addition to the disilene (Scheme 3-6B) and bond insertion
reactions (Scheme 3-6C; see below) occur to give oligosilanes of various types
(see also Scheme 3-5).

Scheme3-6

The reactivity of silylenes is exemplified by the behavior of 3-11. In spite of

the steric protection provided by the Cp* groups, the kinetic stability of the first
“stable” silylene 3-11 is rather low. It reacts readily with many reagents,
including almost anything possessing a lone pair. Some of these reactions are
summarized in Scheme 3-7.58 A consistent theme demonstrated by these
reactions is the tendency for silicon to return to the more stable tetravalent state.

3.7.2-1. Insertion Reactions Silylenes insert into relatively weak bonds (Si-Si,
Si-H), or into stronger bonds when a heteroatom silicon bond will be formed
(0-H, O-Si56368).69Calculations suggest that insertion reactions proceed by
46 SILICON-BASED REACTIVE INTERMEDIATES

s s
\ /
SIR,

Scheme 3-7

initial formation of a donor-acceptor complex, followed by a [ 1,2]-atom shift

(Scheme 3-8). The propensity for bond insertion is one of the complicating
factors in working with silylenes. Once they have been generated by some
means, they may react with both starting materials and products. Some examples
of typical silylene insertions follow.

Scheme 3-8

1. S i - 0 Insertion: Silylenes generated from 3-15 insert into Si-0 bonds,

leading to higher-order oligosilanes (Scheme 3-9).70

3-15

Scheme 3-9

2. Si-H Insertion: This is one of the standard reactions used to prove the
presence of silylenes (Eq. 3.4).'9723731,71,72
The relative reactivity for the
 SILYLENES (RzSI:) 47

insertion is highly dependent on the substituents on the silylene silicon:

The barrier to reaction is higher for silylenes bearing electronegative
substituents (Eq. 3.5).24*73

:SiR, + Et,SiH - R,Si:

H

SiEt,
(3.4)

relative reactivity H2Si :> ClHSi :> HFSi :>> C12Si :, F2Si : (3.5)
3. O-H Insertion: Silylene insertion into O-H bonds leads to synthetically
useful difunctional silanes: The Si-H and Si-OR functional groups that
are found in the products will react under different conditions (Eq. 3.6, see
Chapters 5 and 7).74

:SIR, 4- ROH - R,Si:

H

OR
(3.6)

4. C-H Insertion: Although perhaps the most interesting reaction in a

synthetic sense, silylene C-H bond insertion is not facile, even at higher
temperatures, although some examples are known (Eq. 3.7).73*75,76

H-H - :Sic$
-H
H
SiCI, (3.7)

5. Oxidation: While not formally an insertion, silylenes are oxidized by N20

to give silanones that, in turn, produce oligosiloxanes [R2Si:+ N20 +
R2Si=0 -+ (R2SiO),].51

3.1.2.2. z-Bond Addition Reactions In addition to insertion reactions with u

bonds, silylenes will react with carbon T systems to form siliranes and silirenes
as noted above.77The siliranes are themselves relatively unstable and may be
used as silylene transfer reagents: They participate in alkene swapping reactions
(Eq. 3.8). However, insertion occurs with reactive alkenes, rather than alkene
exchange (Scheme 3-3C, Eq. 3.9). In special cases, such as with sterically
encumbered ~ i l y l e n eor
s ~alkenes
~ (or d i e n e ~ ) ?the
~ resulting siliranes are rather
stable. One example is shown, 3-16, resulting from multiple additions to an
aromatic compound (Eq. 3.10). Dimesitylsilene adds to hindered ketones to
produce an oxasilacyclopropane that was characterized by an X-ray crystal
structure.80
Silylenes add to dienes to give silacyclopentenes (Scheme 3-4). Concerted
1,2-addition of the silylene to one of the double bonds produces a silirane,81
which then undergoes a vinyl-cyclopropanerearrangement with ring expansion
(Scheme 3-10).78*82The stereoselectivity of the formation of the reaction
products, and trapping experiments, were inconsistent with the alternative 1,4-
concerted-addition process.53383 The 1,bsilylene addition to an a,p-unsaturated
ketone has also been
48 SILICON-BASED REACTIVE INTERMEDIATES

Silylenes will also add to other 7r systems such as is on it rile^^^ and

. ~ ~addition of silylenes to ketones leads to siloxiranes that then
i s o ~ y a n a t e sThe
undergo H migration to give silyl enol ethers.86

Me,Si

Me,Si

(Me3Si)2CH

(Me,Si),CH y+- CH(SiMe,),

CH(SiMe,),

CH(SiMe,),

0 I
CH(SiMe,),

3-16

(3.10)

Scheme3-10

An unusual reaction that involves the formal participation of silylenes is the

Pd-catalyzed reaction of trisilanes with alkynes. The trisilane is converted
primarily into the cyclic disil lalkene dimer along with small amounts of the
linear trimer (Scheme 3-1 1).8 7

3.2. Silylium Ions (R3Sif)

As will be presented in Chapter 5, the silicon in organosilanes generally
undergoes reactions as an electrophile, as a result of its low electronegativity.
Thus the most important reactive intermediate in silicon chemistry should be the
silicon analogue of a carbocation (the terms silicenium or silylenium ions may be
 SILYLENES (R2SI:) 49

\ /
\I + Me,SiCI,
CI,
Si
-Si.
Si
.CI + R+R R,R
catalyst R,R R,R’
/ \ I\ R‘
/ \ +A
CIMe,Si
Si
*SiMe,CI
/ \
Scheme 3-11

supplanted by the term silyliurn ion88).89 These species occur frequently

(ubiquitously) in the gas phase under mass spectrometric conditions (i.e.,
strongly ionizing conditions with low counterion concentration^).^^ Calculations
and mass spectral experiments indicate that silyl cations are more stable than the
isomeric silyl-substituted carbocations (see also Chapter 14).91However, they
are rarely seen in a condensed phase.
A carbocation is usually generated in one of three ways: (1) by complexation
of a halogen atom by a Lewis acid (Eq. 3.1 1, e.g., in a Friedel-Crafts alkylation);
(2) by the addition of an acid, with a non-nucleophilic counterion, to an alkene
(Eq. 3.12), or (3) by abstraction of H- from carbon (Eq. 3.13). Why has it been
so difficult, by comparison with carbon, to isolate a silicon cation? The longer
bonds of silicon make it more susceptible to nucleophilic attack than carbon. In
addition, silicon forms much stronger bonds than carbon with many of the
elements to its right on the periodic table, especially the halo ens and oxygen;
silylium ions have a “voracious appetite” for nucleophiles?’ Thus, the route
using the chemistry found in Eq. 3.1 1 does not lead to the preparation of silylium
ions. Olah and coworkers found, for instance, that even under very favorable
condition, it was not possible to perform a Fridel-Crafts silylation of benzene
(Eq. 3.14)93 although this reaction has been reported in the gas phase.94

(3.11)

HX
K
\
* C
t’
+ X- (3.12)
I

(3.13)

Me,SiCI SiMe,

AICI, (3.14)
“Me,Si’“
<I%
The route in Eq. 3.12 involving silenes, the silicon analogues of alkenes, is
quite attractive. However, stable silenes have only recently been prepared and
isolated (see below) and are, therefore, rather difficult to come by. Further
50 SILICON-BASED REACTIVE INTERMEDIATES

compromising this approach is the fact that silenes are even more susceptible to
nucleophilic attack than tetrahedral silicon.
In contrast to Eqs. 3.11 and 3.12, the route shown in Eq. 3.13 looks quite
attractive for the preparation of a silylium ion. Thermodynamically, a more
stable cation results from a less stable cation, and very non-nucleophilic
counterions may be used in the reaction. Many attempts have been made to use
this chemistry for the preparation of silicon cation^.^' Preeminent is the work of
Lambert and co-workers. The claimed to prepare (i-PrS)3Si+:6 and later
the free triphenylsilylium ionJ7 (using an experiment suggested by Corey,
Eq. 3.15).98
Conductivity measurements were used by Lambert to support the claim that a
silylium ion had been prepared in solution: Conductivities of 1.13 cm2 m o h d
mol in H2CCl2and 179.5 in CH3CN were observed. However, these claims were
aggressively questioned in a series of papers by Olah and co-workers, who noted
the I3C NMR chemical shifts were small, 29SiNMR data could not be observed,
and the X-ra structure shows Ph3SiOC103 to be a covalent tetrahedral
molecule?971d01ah believes the conductance resulted from partial hydrolysis of
the silyl perchlorate. In a similar vein, Eaborn has shown that the solvolyses of
some very hindered silyl perchlorates are extremely slow. The fact that
hydrolysis is slow even in the very ionizing solvent HOCH2CF3suggests that

Ph,SiH + Ph,C+ -CIO, -

R3Si+ is not actually formed in these experiments (Scheme 3-12).'"
Ph,Sf -C104 + Ph,CH (3.15)

Me0
1
Me-Si-Me
(Me,Si),C
I
c---
MeOH

slow solvolysis
0,CIO
\
Me-Si-Me
'
-CF,CH,OH

slow solvolysis
CF,CH,O,
Me- Si - Me
(Me,Si),C

Scheme 3-12

The silatropylium ion (C&H7+) has been shown to be more stable than the
Ph-substituted silyl cation (PhSi Me;?)in the gas phase.lo2Therefore, Olah tried
+

to make the silatropylium ion in solution (Eq. 3.16). It was also found not to be a
free cation. All this evidence suggests that the putative silylium ions of Lambert
were stable neither in solution nor the solid phase, and rather were tetraco-
ordinate silicon species. loo

H OCIO,

The criteria for establishing the presence of a silylium ion are varied,
including a high, positive 29SiNMR shift (225-380 ppm),lo3complete planarity
at silicon, and 120" C-Si-C bond angles. The ability to prepare such silylium
ions clearly depends on the ability to develop and utilize counterions that have
 SILYLENES (R&) 51

9 9

Figure 31. X-Ray Structure of (A) (i-Pr)3Si

+ -Br6CB11H6;(B)Et&i + -B(C6F5)4-C6H5CH3.

much less nucleophilicity than perchlorate. Reed and co-workers utilized the
bulky, non-nucleophilic counterion Br&B 1H6- with i-Pr3Si-I- 3-17 (Figure
3.lA).lM Lambert similarly demonstrated this principle using (F5C6)4B- as a
counterion to Et3Si+.lo5 In the latter case, instead of coordination by the
counterion (F5C6)4B- , the solvent for the crystallization, in this case toluene,
acted as a donor to Et,Si+ (3-18, Figure 3.1B). This makes evident both the
higher electrophilicity and steric accessibility of silicon when compared to
carbon. On the basis of the criteria noted above (average C-Si-C = 114-1 17”,
29
Si NMR = 90- 115ppm), these systems approach true silicon cations: Reed
estimates about 36-52% silylium ion character for his compound.’03The 29Si
NMR chemical shift of i-Pr3Si+ X- has now been established as a convenient
scale for the degree of silylium ion character.lo6In neither of these two structures
are the criteria for a true silylium ion quite met. It has been argued by Schleyer
and Apeloig that Lambert’s complex is a Wheland intermediatelo7 and not a
silylium ion at all. lo* However, we have seen that Friedel-Crafts reactions with
chlorosilanes do not lead to aromatic silylation (Eq. 3.14). Similarly, this
putative “Wheland intermediate” does not lead to electrophilic silylation of the
aromatic system. Thus, experimentally, 3-18 behaves as a weakly solvated
cation. The debate has been nicely summarized by Houk.”’
Lambert and Zhao have more recently described the trimesitylsilylium ion
3-19, which has a 29Si NMR chemical shift of 225.5ppm (Eq. 3.17).’1° This
value is within the predicted range for a silylium ion”’ and has been so
proclaimed.’ l 2 In this case, presumably, the bulkier ligands on silicon preclude
association between solvent and silicon. The preparation and characterization of
such an electron-deficient silicon compound in a condensed phase is a notable
synthetic achievement. It is to be hoped that an X-ray crystal structure of this
compound can be obtained to finally put this debate to rest.

3-19 (3.17)
52 SILICON-BASED REACTIVE INTERMEDIATES

3.3. SlLYL RADICALS (R3Si')

Silicon-based radicals' 13*' l4 are very reactive species that have been much less
studied than the other reactive intermediates described in this chapter (see also
Chapter 7)."5*116They may be somewhat stabilized by adjacent 7r system^."^
However, unlike carbon radicals,'" alkyl and aryl substituents do not provide
substantial stabilization to silyl radicals." By contrast, adjacent silyl groups' l9
and electropositive substituents'20 do stabilize silyl radicals. There are few
examples of isolated silyl radicals, not surprisingly. One important exception is
the radical (Et3Si),Si' that persists for greater than one month at room
temperature!12'
There are relatively few reports of the utilization of radical-based silicon
chemistry in organic synthesis, with the exception of hydrosilylation of C=C and
C=O bonds, although this situation is changing (see Chapters 7,8,and 12). In a
sense, the situation is similar to the case in carbon chemistry some decades ago,
when prevailing wisdom suggested that the gulf between selective synthesis and
radical chemistry could not be brid ed. That situation has now dramatically
changed for carbon-based radicals. 12' Given the current state of knowledge of
silyl radicals, a similar change may be expected in the application of their
general utility in organic synthesis.
One notable feature of silicon radicals is the degree to which they react
stereoselectively. Unlike carbon radicals, which do not maintain their
stereoidentity, silicon radicals retain the chirality of their precursor to a
remarkable degree."3*'23 Thus Brook and Duff showed that the chiral
acylmethyl-a-naphthylphenylsilane underwent photolytic decomposition and
radical trapping by CCl, with 64% e.e. (Scheme 3-13).'24 Similarly, Sakurai,
Kunada, and co-workers showed that an optically active hydrosilane could
undergo radical chlorination in CC14, initiated by benzoyl peroxide, with
retention of c~nfiguration.'~~

"%,

Ph'?
-;i -hv
CCI,
I%,,

ph'?*
NP
- CCI, '%,.

Ph'si
.CI

NP
64% e.e.
Scheme3-13

3.3.1. Generation of Silyl Radicals

Silyl radicals may be generated by several routes analogous to those practiced in
carbon chemistry, including hydro en abstraction from silicon by oxygen (Eq.
3.1 8) 119,126,127 or carbon radical^'^.'^'
(see also Chapter 7). It is generally
observed that abstraction by oxygen radicals occurs at higher rates than for
carbon radical^.'^' For instance, rate constants for hydrogen abstraction from
R3Si-H by t-BuO' at room temperature are on the order of lo7 M-' s-',
whereas rate constants are 3-4 orders of magnitude lower for abstraction by
 SlLYL RADICALS R3SI' 53

R'CH;. These effects have been clearly discussed in the context of carefully
tabulated rate data.' 13~131The special case of radical chain reactions initiated by
azobisisobutyronitrile, using persilylhydrosilanes (Eq. 3.19), will be discussed
in detail in Chapter 7. Silyl radicals may also be generated by the photochemical
decomposition of N-silylazo compounds (Scheme 3-14).'32

0 (3.18)
R3SiH 0 t R3Sio + oo)(Ph + ,,Ao,
hv or A 0

Me3Si,SiMe3

Me3SiNSi\H
+ A C I -
A~BN Me3Si,SiMe3

Me3Si'
si
'CI
+ A H
AlBN =

NCY"""

(3.19)
R3Si/N\"/SiR3 .-= hv N, +
Scheme3-14
2 R3Si* - CCI,
2R,SiCI

The photolytic decompo~ition~~ of di-'33 and polysilanes leads to the

formation of silyl radicals (Scheme 3-15134).22Note that the photolysis of di- or
polysilanes can also lead to silylenes and silenes (see discussions on silylenes,
above, silenes, below, and polysilanes, Chapter 11). Bulky groups, in particular,
favor the generation of radicals over silylenes from phenyldisilanes.135~136Bulky
silyl radicals may also be prepared by the reduction of halosilanes, oxidation of
silyl anions, or by the direct thermolysis of disilanes. The success of these
reactions may be attributed to the kinetic stability of the radical species formed
(Scheme 3-16).13' Depending on substitution patterns and reaction conditions,
the photolysis of acylsilanes (see also Chapter 15) can lead to silyl radicals
(Scheme 3-13).13' Finally, bis-trimethylsilylmer~ury'~~ will undergo photolytic
decomposition to give trimethylsilyl radicals (Eq. 3.20).'40*'4'While the pre-
paration of the mercury compound is relatively facile, the toxicity associated
with mercury compounds limits their attracti~eness.'~~

+
0

Scheme 3-15
54 SILICON-BASED REACTIVE INTERMEDIATES

CN
I
TCNE = " F C N
CN

Oxidation
1
TCNE

Scheme 3-16

(Me,Si),Hg - hv 2 Me$' + Hg (3.20)

3.3.2. Radical Reactions: Addition to x Systems

The rates of some reactions of silyl radicals have been reported."39143As was
suggested in the examples above (e.g., Scheme 3-13 and Eq. 3.19), halide
abstraction by silicon radicals is a very facile process, with rate constants in the
range of 105-10'0 M-' s-' at 200C."~In some cases, particularly in the
z
chlorination of a h drosilane, reaction can occur in the absence of radical
catalysts (Eq. 3.21 ). Synthetically, however, this is an uninteresting reaction
in most cases.

Me$,

Me$'
SiMe,
I
Si
'H
+ C T C I
CI
- Me$,

Me$'
1
SiMe,
Si
'CI
(3.21)

Far more interesting than the formation of halosilanes, in a synthetic sense, is

the construction of hydrolytically stable Si-C bonds, for instance, in a h dro
silylation reaction using silyl radicals (Scheme 3-17, see Chapter 12).14?
rate constants for addition of silyl radicals to alkenes, includin polymerizable
olefins, range from about lo5 to lo9 M-' s-' at 20°C. '"J'
Other radical
additions to double bonds have been demonstrated, including the cyclization
of silahexenyl radicals (Beckwith cyclization146~147for related reactions with
silicon-stabilized carbon radicals; see Chapters 8 and 14).'26 Unlike the
hydrosilylation reaction catalyzed by transition metals (with H2PtC16as catalyst,
the product ratio of five-ring to six-ring 94.6 :5.4 was observed; see Chapter 12),
six-membered ring products are favored over the five-membered isomer (Eq.
3.22). 114~126The free radical addition of hydrosilanes to carbonyl groups has also
been reported.' 13~140~148~149The reaction works reasonably well with electron-
 SlLYL ANIONS (R3Si-) 55

HSiX, -. -t-BuOO-t-Bu
Six, H

Scheme 3-17

deficient silyl radicals (e.g., C13ST),’50 although hydrosilylation of both alkenes

and ketones is more frequently practiced using a transition metal catalyst (see the
section on the reduction of carbonyls in Chapter 7).

+
(3.22)
135% 0.65 5.46

Catalyst 30QC 1.47 9.48

Silyl radicals will perform substitution reactions on aromatic systems. For

instance, the reaction of hydrosilanes with benzene in the presence of peroxides
leads to arylsilanes (Eq. 3.23).15*Leaving groups from the aryl ring include H,
SiR3, and halides. One rather esoteric example of this process is the addition of
two silicon radicals to C60to give both monomeric and polymeric species. The
latter can be envisaged to be a “string of pearls” with catenated Si-Si chains as
the string and Cm as the pearl (Eq. 3.24).lS2

+ Et,SiH

Ar Ar
I 1
-I
Ar- Si Si -Ar
I
Ar- Si - Si -Ar
-hv
Ar-
Ar Ar
I
Ar-Si-.
Si-Ar

-Si -Q-Ar
I I
a
Ar =a
Ar Ar Ar

(3.24)

3.4. SlLYL ANIONS (RSSJ-)

The silicon community has not exercised the same degree of rigor in examining
the structure of silyl anions, when compared to silyl cations. In the gas phase,
56 SILICON-BASED REACTIVE INTERMEDIATES

free silyl anions have been generated by a variety of In

condensed phases, however, it is generally assumed that polarized bonds
between silicon and alkali or alkaline earth metals are "silyl anions." It is not
clear that truly ionic silyl anions have been prepared: This remains a synthetic
challenge. Having recognized its deficiencies, we too will follow this protocol.
There are many examples of compounds in which alkali'54 and other metals
are bonded directly to ~ i l i c o n . ' ~There
~ , ' ~ ~is also a large literature of silicon-
transition metal a-complexes, an overview of which may be found in Chapter 6.
As with the analogous carbanions, the shift towards monomeric'57 species is
aided by the addition of chelating agents such as ethers (DME, THF), amines
(TMEDA), and related compounds (HMPA, DMPU) that break up aggregate^.'^'
Silyl anions tend to retain their chirality: A lower limit to the barrier for
inversion of the anion (i-P~-)~Phsi- Li+ has been set at ca. lOOkJmol-'
(24 kcal m01-').'~~

3.41. Preparation by Metal-Halogen Exchange and Other Metalations

The historical route to silyl anions utilized metal-halogen exchange at silicon
with mercury (Scheme 3-18);'60*'61Si-H16* groups can also be converted into
Si-Hg groups. Once prepared, the mercury may be exchanged with other metals
(Scheme 3-18).'63 Mercury compounds, as has already been noted,'42 may be
rather toxic, and other ways to prepare silyl anions have, therefore, been sought.
One does not need to resort to the use of mercury salts when anion-stabilizing
groups are present on silicon. In these cases, direct metal-halogen exchange is an
efficient process for preparation of the anion. Some examples include arylhalo-
silanes, which undergo metal-halogen exchange with potassium'64 or lithium
(Scheme 3-19),'65 and tris(trimethylsily1)bromosilane [(Me3Si)3SiBr PhLi + +
+
(Me3Si)3SiLi PhBr]. 166 These metalations are heterogeneous and may be
accelerated by sonication. In the case of silole derivatives (silacyclopenta-
d i e n e ~ ) , the
' ~ ~dianion can be formed and then alkylated or silylated (Scheme
3-20).'68*'69Aside from the limited types of examples presented here (see also

Me,SiCI -Na I Hg
(Me,Si),Hg

Scheme 3-18
- Li
2 Me,SiLi

Red solution
Scheme 3-19
 SlLYL ANIONS (R3Si-) 57

(3Ph4

CI Osi.CI
- 3 ~ iTHF
,
sonication
B p h

.
Li 0 si Li
4 Me,SiCI

Me,Si
oph4

'Si .SiMe,
Scheme 3-20

the discussions on silylene-type intermediates, above, and disilenes, below),

metal-halogen exchange is not a general method for silyl anion synthesis.
Silyl anions may be prepared by the cleavage of relatively weak bonds,
notably Si-H and Si-Si (Eq. 3.25).l7' Normally, it is necessary to add a strong
metal chelating agent such as TMEDA or HMPA to complex the counterion.
Some concern has been raised about the mutagenicity of HMPA.I7l However,
related solvents that are not mutagenic, such as DMPU, have similar solvating
proper tie^.'^^ Note that in the absence of such agents, very different chemistry
can arise, involving nucleophilic substitution of hydride rather than deprotona-
tion (Eq. 3.26).'73

I HMPA DMPU
(3.25)

Ph,SiH - MeLi
Ph,SiMe + LiH (3.26)

An alternative preparative route to silyl anions utilizes the reductive (Eq.

3.27)'59,'74or nucleophilic (Scheme 3-21) cleavage of disilanes by MeLi'75 (an
improved synthetic procedure has been reported by Hudrlik et ~ z l . ' ~KH,"'
~),
KOMe, or F-.'77 Unless there is an aromatic group on silicon, HMPA or
TMEDA is frequently required as co-solvent: In some cases a polar ether solvent
such as THF or DME suffices. 1,2- or 1,3-dilithiotrisilanescan be prepared by

-
the ring-opening, reductive cleavage of cycl~trisilanes.'~~
SiR,Ar Li
ArR,Si ArR,SiLi (3.27)

The existence of sila-Grignard reagents has often been the subject of

speculation. The determination of the crystal structure of an amine-stabilized
Grignard complex has conclusively proven their existence (Me3SiMgBr
Me2NCH2CH2NMe2). 154~179Methods for their generation include the transme-
talation of alkyl- or arylsilyllithium species, such as Ph3SiLi,with MgBr2"' and
transition metal complexes with MeMgBr (Scheme 3-22).18'
The silyl anions shown above have three nonfunctional spectator ligands (i.e.,
R3Si-, R = alkyl, Ar,etc.). One would like to have access to functional silyl
anions as a route to more complex molecules. Silyl anions bearing silyl ligands
58 SILICON-BASED REACTIVE INTERMEDIATES

Me,Si-SiMe, - KH
HMPA
Me,SiK + Me$

KOMe
Me,Si-SiMe, Me,SiK + Me,Si LJ

Me,Si-SiMe, -Bu,NF
Me$-
+ NB~,
+ Me,SiF

Scheme3-21

Me,SiCI + "Mg" -[ Me,SiMgBr] Me,SiSiMe,

Ph,SiLi + MgBr, - Ph,SiMgBr

MeMgBr
(CO),CoSiPh, Ph,SiMgBr
Scheme 3-22

(RMe2SiSiR'MeLi), which might be useful for the synthesis of well-defined

polysilanes and oligosilanes (see Chapter lo), have been
Although C13Si- and (RO),Me3-,Si- have been postulated as unstable
intermediates, they have not yet been isolated.18'
It is now possible to prepare silyl anions that possess additional
f~nctionality.'~~Metalation, using lithium, of compounds such as 3-20leads
to silyl anions 3-21(Eq. 3.28) that display both nucleophilic and electrophilic
properties (Scheme 3-23; see below). Such anions may also be enerated from
chlorosilanes using lithium 1-(dimethylamino)naphthalenide.lf4 Ito and co-
workers have extended their study of silyl anions to include alkoxy-substituted
species 3-22.85
CI Li Ph
Ph, 1 .NE$ Li (dispersion) Ph, I ,NE$ Li, I ,OR
Si *
I si si (3.28)
Ph THF, O°C, 4h Ph Ph
3-20 3-21 3-22

56%
SiPh,NEt, Si Ph,O-i-Pr

Scheme 3-23
 SlLYL ANIONS (R3Si-) 59

3.4.2. Reactions of Silyl Anions

Silyl anions are good nucleophiles and behave in an analogous manner to the
corresponding carbon species; that is, they abstract protons or act as nucleophiles
(see also Cha ter 12). For instance, silyl anions may be used to make
acylsilanes.186*ps7The yield is profoundly affected by the metal counterion, a
trend we shall see below in more detail (Scheme 3-24)'*? The presence of
copper, in particular, frequently leads to higher yields. The resulting
a ~ y l s i l a n ecan
' ~ ~ be further manipulated, with ultimate loss of the silicon, for
the purposes of organic synthesis (see Chapters 12 and 15).
0 0
0
- -
.A
A Ph,SiM
CI
M = Li
Cul
0

SiPh,

8% > 90%
Scheme3-24

In the absence of stabilizing groups, silyl anions react like Grignard reagents
with carbonyl compounds. Nucleophilic attack generates the a-silylalkoxide,
which can be isolated as the a-hydroxysilane after acid workup (Scheme
3-25A). When the carbonyl group bears stabilizing groups (electron-with-
drawing groups), however, the resulting alkoxide 3-23 can undergo further
reaction via a [1,2]-silyl migration from carbon to oxygen (Brook rearrange-
ment; see Chapter 15) to give stabilized carbanion 3-24.Hydrolysis in this case
leads to the alkoxysilane or its hydrolysis products (Scheme 3-25B). Note that
adventitious proton sources can quench the alkoxide 3-23 to give the simple
carbinol3-25 prior to rearrangement.
n

".Y = Ph

+
'rc Ph
H,O. ROH
\ or other proton source

Scheme 3-25
60 SILICON-BASED REACTIVE INTERMEDIATES

a,P-Unsaturated carbonyl compounds undergo conjugate (Michael) addition

by silyl anions. For example, Still and co-workers demonstrated that Me3SiLi
would undergo conjugate addition to unhindered, but not to hindered, a,&
unsaturated ketones (Scheme 3-26)'75: Fleming and co-workers demonstrated
that silyl copper com lexes were less sensitive to steric constraints than their
lithium counterparts. The resulting p-silyl enolates can undergo stereo-
selective a l k y l a t i ~ n . ' ~ 'For
~ ' ~ instance,
~ in the synthesis of dihydrojasmone,
(PhMe2Si)2CuLiadded efficiently to cyclopentenone 3-26 to give an enolate that
could be trapped by Me3SiC1. Subsequent aldol and desilylation reactions led to
the target structure (Scheme 3-27).'93 The phenyl group is required to facilitate
desilylation (see Chapter 8). Hydrodesilylation (the terms proto- and
protiodesilylation are also commonly en~ountered)'~~ of the phenyl group gives
a fluorosilane that is readily cleaved from the carbon skeleton by oxidation.
These reactions will be covered in more detail in Chapters 14 and 16.
The functional silyl anions described a b ~ v e ' * ~ exhibit- ' ~ ~ a similar nucleo-
philic chemical reactivity to simple silyl anions. However, in addition to acting
as nucleophiles, they themselves are susceptible to nucleophilic attack. The
reaction between 3-21 and chlorosilanes, for example, leads to Si-Si bond
formation: The stabilizing amino group can be readily displaced by alkoxy or
other groups. These anions are useful alcohol synthons in organic chemistry. For
example, following conjugate addition to an a,p-unsaturated ester, enolate
alkylation, mild alcoholysis, and oxidation complete the formal, stereoselective
addition of H3C+OH to the alkene (Scheme 3-28A). The analogous SN2'

No Reaction -
b
OLi si,: ' .

-
OSiMe, ""l

SiMe,

Scheme 3-26

,SiMe,
(i)(PhMe,Si),CuLi

Scheme 3-27
 Next Page

x BONDS TO SILICON 61

OH
pNPh,SiLi
C 0' -8 E&NPh,SiCuCN
D Li
OH

SiPh,NEt,

Scheme 28

displacement of a carbamate by these functional anions has also been described

(Scheme 3-28B).lg5Finally, the effect of the metal counterion can be seen from
the different regiochemistry of attack of an a,P-unsaturated epoxide in the
presence and absence of copper (Scheme 3-28C, D).'96

3.5. II: BONDS TO SILICON

Silicon forms ( p - p ) n bonds only with difficulty. Prior to the 1970s, it was
generally understood that, with the exception of carbon, Group 14 elements
could not form stable double bonds.6 It was believed that the poor overlap of p
orbitals, due either to large distances between atoms (e.g., Si-Si) or to poor size
match (e.g., Si-C), precluded favorable bonding interaction^.'^' However,
during the 1970s it became evident that such species could be prepared in the gas
phase and then trapped. In 1981, the first crystalline examples of compounds
containing Si=Si8 and Si=C7 bonds, res ectively, were isolated; many examples
have been reported subsequently.49*198~1g9When compared with carbon, such T
bonds are not particularly strongzm and, more important, are kinetically very
reactive. As has been noted, the increased length of bonds to sp3-hybridized
silicon makes it much more susceptible to nucleophilic attack than carbon. This
is even more true for sp2-hybridized silicon. We will briefly review the
preparation, structural characteristics?" and reactivity of the most important of
these species, the disilenes Si=Si?02 silenes Si=C, and silanones Si=O. Other
multiply bonded species (Si=N, Si=S, Si=P, etc.) will be noted.