Pentacoordinate hydrochlorosilanes with lactamomethyl ligand

Article abstract of DOI:10.1016/j.jorganchem.2007.01.035

The synthesis and reaction behavior of pentacoordinate hydrochlorosilanes LCH₂SiRHCl (L- 2-piperidonyl ligand, R = Me, Ph, Bn) are described. The intramolecular O-Si and N-Si coordination is discussed on the basis of the NMR data. The strength

Full text of DOI:10.1016/j.jorganchem.2007.01.035

Journal of Organometallic Chemistry 692 (2007) 2160–2167
www.elsevier.com/locate/jorganchem
Pentacoordinate hydrochlorosilanes with lactamomethyl ligand
z
*
Vadim A. Pestunovich , Svetlana V. Kirpichenko , Natal’ya F. Lazareva,
Aleksander I. Albanov, Mikhail G. Voronkov
Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russia
Received 14 November 2006; received in revised form 17 January 2007; accepted 22 January 2007
Available online 30 January 2007
Abstract
The synthesis and reaction behavior of pentacoordinate hydrochlorosilanes LCH2SiRHCl (L- 2-piperidonyl ligand, R = Me, Ph, Bn)
are described. The intramolecular O–Si and N–Si coordination is discussed on the basis of the NMR data. The strength of the O–Si
coordinate bond is nearly the same for chelates 5, 6, 8 irrespective of the equatorial substituent R at the silicon atom. However, the nat-
ure of R substituent markedly affects the stability of the complexes with the N–Si intramolecular bond.
ꢀ 2007 Elsevier B.V. All rights reserved.
Keywords: Pentacoordinate silicon compounds; Silicon hydrides
1. Introduction
equatorial position has no profound effect on the Si–O
hypervalent bonding in pentacoordinate chelates bearing
acetamidomethyl or lactamomethyl ligands. Pentacoordi-
nate (O–Si) complexes LCH2SiMeF2 derived from N-
methylacetamide [10], N-(1-phenylethyl)acetamide [11],
piperidone-2 [10] and hexahydroazepinone-2 [11] have sim-
ilar 29Si chemical shifts (55.5 ppm). The differences in the
coordination shift Dd29Si for related pentacoordinate
monofluoro and difluoro compounds are small (1–2 ppm).
This indicates that the fluoro derivatives are not susceptible
to changes in the amide ligand [12] and the presence of the
second fluorine atom at silicon.
Pentacoordinate organosilicon compounds with ami-
domethyl or lactamomethyl ligands having the O–Si dative
bond have been the subject of extensive synthetic and struc-
tural investigations [1–7]. The results of these studies made
an important contribution to the understanding mechanism
of the nucleophilic substitution at silicon [1,2,4,5,8]. It has
been found that the extent of the O–Si intramolecular bond-
ing in pentacoordinate monofunctional silanes LCH2Si-
Me2X (L – amido or lactamo donor group) depends on
the nature of the donor amide group as well as the electro-
negativity and the leaving group ability of the axial ligand X
(X = halogen, OAlk, OAr, OTf) [1,4]. The presence of the
electronegative ligand in the equatorial position results in
strengthening the oxygen-silicon coordination. Thus, the
O–Si and Si–Cl axial bonds become shorter on going from
N-(dimethylchlorosilylmethyl)- to N-(methyldichlorosilyl-
methyl)hexahydroazepinone-2 [9]. Nearly the same effect
is observed by changing the methyl group by a methoxy
group [9]. However the presence of a fluorine atom in the
There are only few data for the variation in non-electro-
negative organic substituents at silicon in amide-type pen-
tacoordinate complexes. By 29Si NMR data, the O–Si
interaction increases by changing the methyl group by the
electron withdrawing phenyl group in monochloro deriva-
tive of N-methylacetamide [13,14] or monofluoro derivative
of N-(1-phenylethyl)acetamide [14]. Introduction of a a-
naphthyl group instead of the methyl one in the ligand
environment at silicon results in shortening the O–Si bond
length (by 0.02 A) [15]. According to X-ray and 29Si NMR
˚
data, replacing two equatorial methyl groups by two elec-
tron-donating trimethylsilyl groups in pentacoordinate
chelate derived from N-methylacetamide does not affect
*
Corresponding author. Tel.: +7 3952 426345; fax: +7 3952 419346.
E-mail address: svk@irioch.irk.ru (S.V. Kirpichenko).
Prof. V.A. Pestunovich who inspired this work deceased July 4, 2004.
z
0022-328X/$ - see front matter ꢀ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.01.035

V.A. Pestunovich et al. / Journal of Organometallic Chemistry 692 (2007) 2160–2167
2161
the strength of the O–Si bond [16]. Although a broad range
of pentacoordinate silicon hydrides were described [2,17–
22], the amide-containing complexes having a Si–H bond
are unknown until now. Meanwhile an additional Si–H
bond provides further potential site for ligand substitutions
that might lead to novel hypervalent silicon compounds.
In this paper, we report synthesis, structure and some
chemical transformations of new pentacoordinate hydro-
chlorosilanes obtained from piperidone-2. Variation in
organic substituents at silicon allowed to study their effect
on the formation of the intramolecular coordinate bond
between the silicon atom and the oxygen or nitrogen atoms
of the bidentate amide ligand.
sample at 40 ꢁC for 1 h. The complete conversion of (7)
into (6) occurs over 2 days at room temperature so that
pure (O–Si) chelate (7) was isolated and characterized.
1
The remained signals in the H, 13C, 15N and 29Si spectra
of the crude product were assigned to (N–Si) chelate (7).
Mechanism of the formation of the (O–Si) chelates have
been studied for the reaction of (1) with ClCH2SiMe2Cl by
1H, 13C and 29Si NMR monitoring at low temperature
(Scheme 2) [1,4,5,23,24]. As was shown previously, sily-
lated amides and lactams can exist in the N- and O-tauto-
mer forms (Scheme 2, A and B structure, respectively).
Their ratio depends on the electronic and steric effects of
the substituents at silicon [25–27]. Compound (1) as well
as the transsilylation product A (R = X = Me) have N-tau-
tomer structure in CH2Cl2 and CHCl3 solutions [4,23,28].
In this case the main reaction pathway involves rearrange-
ment of A into O-silylmethylated compound C at low tem-
perature (ꢀ20ꢁC). The latter proved to be quite unstable at
room temperature and readily converted into N-silylmethyl-
ated chelate D within 5-10 min [1,23,24]. Similar successive
reaction sequence can be suggested for the formation of the
(O–Si) pentacoordinate chelate (5).
2. Results and discussion
2.1. Synthesis
The pentacoordinate hydrochlorosilanes (5–8) were pre-
pared by transsilylation reaction of N-trimethylsilylpiperi-
done-2 (1) by the appropriate (chloromethyl)silane
derivatives ClCH2SiRHCl (2–4) (Scheme 1) using the
method described previously [1,5–7]. The reaction product
depends on the nature of R substituent. Thus, methyl(chlo-
romethyl)hydrochlorosilane (2) reacts readily with (1) in
hexane at room temperature to afford (O–Si) chelate (5)
in high yield (65%). Reaction of (1) with phenyl substituted
silane (3) gave a 4.5:1 mixture of isomeric pentacoordinate
Replacement of the methyl group by the electron-with-
drawing phenyl group increases the population of O-sily-
lated imidate (structure B) [27]. In this case the reaction
proceeds via parallel conversions of the corresponding N-
and O-transsilylated tautomers A and B into (N–Si) and
(O–Si) chelates (7) and (6), respectively. Moreover, chelate
(6) with the O–Si intramolecular bond arises mainly from
O-silylated tautomer that is confirmed by appreciable sta-
bility of chelate (7) at room temperature. Such a way to
the (O–Si) pentacoordinate complexes has been previously
proposed as minor one for X = R = Me [1,23,24]. The imi-
date form, apparently, becomes more unfavorable on going
from the phenyl to the benzyl derivative. As a consequence,
benzyl substituted chelate (8) is formed via pathway
A ! C ! D as in the case of chelate (5).
1
chelates (6) and (7) in 87% yield. It follows from the H
NMR spectrum of the crude reaction mixture which shows
two sets of resonance with similar chemical shifts. The
minor and major components were assigned to the (N–Si)
and (O–Si) chelates (7 and 6, respectively) by comparison
1
of their H, 13C and 29Si NMR data with those for (N–
Si) and (O–Si) dimethyl(chloro)silylmethyl chelates [23].
Compound (8) with the O–Si coordinate bond was
obtained as the sole product from similar reaction of ben-
zyl substituted silane (4) with (1).
To have a better understanding of the possible routes of
the formation of complex (6), the reaction between N-silyl-
lactam (1) and hydrochlorosilane (3) was monitored by 1H
and 29Si NMR spectroscopy. When a 10% w/w solution of
compound (1) in CDCl3 was titrated with sufficient amount
of (3) at room temperature, the simultaneous appearance
of two sets of the chemical shifts in a 2.5:1 ratio for the che-
lates (6) and (7) are observed. Predominance of (6) over (7)
became considerably higher (5.6:1) after heating the NMR
Compound (7) is the first example of stable at ambient
temperature pentacoordinate complexes of the O-imidate
structure. Previously related stable complexes were
described for germanium and tin derivatives [5,29–31].
+ ClCH2SiRXCl
X
- Me3SiCl
OSi
N
O
N
O
N
R
X
R
SiMe3
SiCH2Cl
CH2Cl
1
A
B
+
ClCH2SiRHCl
+
- Me3SiCl
2-4
N
O
N
O
N
O
H
R
H
R
SiMe3
Si
Cl
Si
N
O
N
O
R = Me (2)
R = Ph (3)
R = Bn (4)
1
X
R
X
Cl
5, 6, 8
7
Si
Si
Cl
R = Me (5)
R = Ph (6, 7)
R = Bn (8)
R
Cl
C
D
Scheme 1.
Scheme 2.

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V.A. Pestunovich et al. / Journal of Organometallic Chemistry 692 (2007) 2160–2167
2.2. Structure and coordination behavior
The 15N NMR resonance for chelate (7) is shifted
upfield relative to the range typical of O-silylated imidates
[25] that is due to the formation of the N–Si intramolecular
dative bond. For chelate (6) the 15N signal (245.4 ppm) is
shifted in lower field as compared with that of piperi-
done-2 (114 ppm) because of increased p-character of the
N–C bond in amide-type chelates [13].
The structure of the novel (N–Si) and (O–Si) chelates (5–
1
8) in solution was determined by H, 13C and 29Si NMR
1
spectroscopy. In the H NMR spectra of chelates (5–8)
the H–Si proton resonances are shifted to lower field (by
0.4–1.3 ppm) relative to those for initial silanes (2–4). The
resonance of SiCH2N methylene protons for all chelates
as well as silanes (2–4) appears as AB quartet due to the
The important 29Si NMR spectroscopic data are pre-
sented in Table 1. The corresponding data for the model
tetravalent silanes are listed for comparison.
1
chirality of the silicon atom. Moreover, in the H NMR
spectra of all chelates coupling H(Si) proton with a trans-
oriented methylene proton results in a further splitting
high-field doublet of AB quartet into two doublets
(3J = 2.5–5.5 Hz).
The 29Si resonances of the chelates (5–8) are markedly
shifted upfield from those of starting hydrochlorosilanes
(2–4) as typical for pentacoordinate silicon compounds
[32]. The J(Si–H) coupling constants for all compounds
are significantly increased to those of the initial tetracoor-
dinate silanes (2–4) that also suggests pentacoordination
at silicon [32,33].
For LCH2SiMeRCl (L-2-piperidonyl ligand) the coordi-
nation shift is greater for R = H (5, Dd29Si = 68.05 ppm)
than that found for R = Me (Dd29Si = 59.98 ppm) [5,6]
indicating stronger O–Si intramolecular bonding in com-
pounds having SiMeHCl fragment in comparison to those
with SiMe2Cl unit. This is the result of the enhanced accep-
tor ability of the silicon atom on the replacement of the
methyl group by a hydrogen atom [17,34,35].
The strength of the O–Si coordinate bond as measured
by the Dd29Si values (Table 1) is nearly the same for che-
lates (5), (6) and (8) with SiCRHCl coordination frame-
work irrespective of the R substituent at the silicon
atom. However, the stability of the (N–Si) chelates is
markedly affected by the nature of the equatorial R
organic group.
1H NMR spectrum of a 4.5:1 mixture of compound (6)
and (7) shows the two signals at 2.93 and 4.08 ppm attrib-
uted to the SiCH2N and SiCH2O units. The H–Si proton
resonance for (7) is observed at higher field relative to that
for (6) (Fig. 1).
As the temperature of the solution of (6) in CD3C6D5
1
increased to 80 ꢁC no changes in the H NMR signals of
SiCH2N protons was observed. This suggests a high barrier
for fluxional ligand exchanges at the chiral silicon atom.
The imidate structure for chelate (7) is supported by the
13C and 15N NMR spectral data. The 13C NMR spectrum
exhibits signals at 57.92 and 172.40 ppm for OCH2Si and
N@C–O groups, respectively. The difference in 13C chemi-
cal resonances of a conjugate unit for chelates (6) and (7) is
small (1 ppm) because of involving one or another hetero-
atom in the coordination bonding. The same difference for
triorganosilylated amides and imidates is considerably
greater (15 ppm) [27].
CH2-6 in 6
SiCH2N in 6
SiH in 6
SiCH2O in 7
SiH in 7
ppm
Fig. 1. Part of 1H NMR spectrum for a 4.5:1 mixture of (6) and (7) in CDCl3.

V.A. Pestunovich et al. / Journal of Organometallic Chemistry 692 (2007) 2160–2167
2163
Table 1
29Si NMR data for pentacoordinate complexes 5–8 and model compounds
in CDCl3 solution (d, ppm; J, Hz)
+ H2O
+ HCl
- H2
- HCl
N
O
N
O
N
O
H
H
OH
Me
Complexes d29Si
J(SiH) Initial silanes d29Si
J(SiH) Dd29Si
Si
Si
Cl
Si
Cl
Me
Me
OH
5
6
7
8
ꢀ64.09 286.44
2
3
3
4
3.96 234.72 68.05
ꢀ5.55 246.34 68.80
77.75
9
5
10
ꢀ74.35 298.7
ꢀ83.30 286.90
ꢀ67.05 298.6
Scheme 3.
1.60 243.10 68.60
urea
i-PrOH/
hexane
(a)
(b)
2.3. Chemical behavior
Me(ClCH2)SiHCl
Me(ClCH2)SiH(OPr-i)
2
13
An enhanced reactivity of Si–Cl bond is typical for
hypervalent silicon compounds compared to tetravalent
derivatives [19]. As a consequence, pentacoordinate hydro-
chlorosilane obtained are susceptible to hydrolysis. Thus,
complex (5) is very sensitive to moisture. Even trace
amounts of H2O in CDCl3 solution results in its partial
i-PrOH/Et3N
heptane
O
O
N
N
Me
Si
Me
H
Si
H
Cl
OPr-i
14
5
1
hydrolysis (ꢁ10%). H NMR spectrum shows the addi-
Scheme 4.
tional resonance of the Me–Si protons (singlet at
0.69 ppm) and the excess integral intensity of the ring pro-
ton signals in reference to that of the Si–H signal. This
points to the formation of hydrolysis product having no
Si–H bond. The gradual decrease in intensity of the H(Si)
anes react rapidly with Bro¨nsted acids without any catalyst
[20]. Initial hydrolysis of the Si–H bond is less likely taking
into account that chlorine is a better leaving group than
hydrogen [17]. Further transformations of silanol (10) have
not been studied (see Scheme 3).
It should be noted that hydrolysis of tetravalent silane
(2) left the Si–H bond intact to give the corresponding di-
siloxane [(ClCH2)MeSiH]2O (d29Si ꢀ9.32 ppm).
1
resonance in the H NMR spectrum of compound (5) is
accompanied by appearance of a new signal at 6.70 ppm
assigned to a silanol group.
Complex (8) is hydrolytically highly unstable and decom-
posed rapidly on exposure to air moisture. As monitored by
1H and 29Si NMR spectroscopy, its hydrolysis proceeds
much faster as compared to that of chelate (5). In the 29Si
NMR spectrum of CDCl3 solution of (8) one new signal
appears at ꢀ67.60 ppm assigned to hydrolysis product. To
avoid hydrolysis in the NMR samples, it is necessary to
use freshly distilled CDCl3 or C6D6. Compared with (5)
and (8) pentacoordinate hydrochlorosilane (6) appears to
be more stable. When the latter complex was kept for one
week under an argon atmosphere in a Schlenk flask with
a rubber septum, rather intensive peak for H(Si) proton
Like initial hydrochlorosilane (2), pentacoordinate che-
late (5) reacts with one equivalent of isopropyl alcohol in
the presence of triethylamine at 0 ꢁC (Scheme 4a, b) to
afford desired monosubstituted isopropoxysilane (14) in
40% yield. The 29Si resonance of this compound shows
small upfield shift (Dd = 10 ppm) relative to that of tetraco-
ordinate silane Me(ClCH2)SiH(OPr-i) (13). Furthermore,
the J(SiH) coupling for (14) is slightly increased in compar-
ison to that for (13). According to these data, a weak O–Si
intramolecular interaction exists in compound (14).
In summary, a series of new amide-type pentacoordinate
silicon compounds with SiOC2HCl framework have been
synthesized. The study of these complexes appears to be
quite promising, because variations in organic substituents
at silicon offer the possibility to prepare stable N–Si com-
plexes unknown so far. Further studies to investigate this
aspect are in progress.
1
was still observed in its H NMR spectrum.
We proposed that the first intermediate detected in the
course of the hydrolysis of chelate (5) was pentacoordinate
chlorosilanol (10). Evidence for this species was obtained
from comparison of its 29Si chemical shift with that for
model pentacoordinate compound, N-(methylisopropoxy-
chlorosilylmethyl)piperidone-2 (12). The latter was
obtained by the reaction of (1) with (ClCH2)SiMeCl(OPr-
i) (11) according to Scheme 1 [36]. Both compounds (10)
and (12) have similar ligand environments at the pentacoor-
dinate silicon atom and closely related 29Si resonances
(ꢀ48.66 and ꢀ52.50 ppm, respectively). Note that varia-
tions in the 29Si chemical shifts from related silanols to alk-
oxysilanes are within limits of 2–10 ppm [37,38].
3. Experimental
3.1. General comments
All reactions and other manipulations were carried out
using standard Schlenk techniques under an argon atmo-
sphere. Diethyl ether and tetrahydrofuran were purified
by distillation from sodium/benzophenone ketyl; n-hexane,
benzene, triethylamine were distilled from calcium hydride.
CDCl3 was distilled from calcium hydride and kept over
Chlorosilanol (10) is presumed to arise from initial con-
version of (5) into hydrosilanol (9) followed by fast H–Cl
exchange due to an enhanced reactivity of the hydrogen
atom in pentacoordinate silicon complexes, as compared
with tetravalent silanes [20,39,40]. Hypervalent hydrosil-
˚
4 A molecular sieves. NCS and piperidone-2 were pur-

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V.A. Pestunovich et al. / Journal of Organometallic Chemistry 692 (2007) 2160–2167
chased from Lancaster and Merck, respectively, and used
without further purification. Melting points were measured
in sealed capillaries. The 1H, 13C, 15N, and 29Si NMR spec-
tra were recorded on a Brucker DPX-400 spectrometer
(1H, 400.1 MHz; 13C, 100.6 MHz; 15N, 40.5 MHz; 29Si,
79.5 MHz) at room temperature. CDCl3 or C6D6 were used
as the solvent. Chemical shifts (ppm) were determined rel-
ative to internal CHCl3 (1H, d 7.27; CDCl3), internal
CDCl3 (13C, d 77.0, CDCl3), internal C6HD5(1H, d 7.28,
C6D6), internal C6D6 (13C, d 128.0, C6D6), or external
TMS (29Si, d 0; CDCl3, C6D6). The 15N chemical shifts
are referred to resonance of CH3NO2 (15N, d 0.0). Analysis
3.3. Synthesis of organyl(chloromethyl)dihydrosilanes
3.3.1. General procedure:
Methyl(chloromethyl)dihydrosilane
Methyl(chloromethyl)dichlorosilane (32.7 g, 0.2 mol)
was added to LiAlH4 (4.5 g, 0.12 mmol) in 100 ml dibutyl
ether at 0 ꢁC. The reaction mixture was allowed to warm
to room temperature and stirred for additional 30 min.
When the resulting white precipitate was settled, the upper
ether solution was decanted to a dropping funnel and added
to 400 ml of 10% aqueous HCl with cracked ice. After stir-
ring for 30 min, the organic phase was separated and the
aqueous layer was extracted with dibutyl ether (2 · 20 ml).
The combined organic extracts were dried over anhydrous
MgSO4 and filtered off. A column distillation afforded
methyl(chloromethyl)dihydrosilane in 40% yield (7.64 g,
0.08 mol) as a colorless liquid, b.p. 59 ꢁC, n2D0 1.4220. Lit.
1
and assignment of the H NMR data were supported by
homonuclear (COSY) and heteronuclear (HSQC 13C–1H,
HMBC 13C–1H) 2D correlation experiments.
3.2. Synthesis of organyl(chloromethyl)dichorosilanes
1
[44]: b.p. 60ꢁC, n2D0 1.4184. H NMR (CDCl3): d 0.31 (t,
3.2.1. Methyl(chloromethyl)dichlorosilane was
commercially available
3H, MeSi, 3J = 4.10 Hz), 2.96 (t, 2H, SiCH2Cl, 3J =
1
3.05 Hz), 3.97 (qt, 1H, SiH). H NMR data are consistent
with the literature data [45]. 13C NMR (CDCl3): dꢀ9.55
(MeSi), 25.91 (SiCH2Cl). 29Si NMR (CDCl3): dꢀ33.80.
Phenyl(chloromethyl)dihydrosilane and benzyl(chloro-
methyl)dihydrosilane were obtained following the same
procedure. Diethyl ether was used as a solvent.
3.2.2. Phenyl(chloromethyl)dichlorosilane
The compound was prepared following a common liter-
ature procedure [41,42].
Phenylmagnesium bromide prepared from magnesium
powder (4.8 g, 200 mmol) and bromobenzene (34.42 g,
200 mmol) in anhydrous Et2O (75 ml) was added dropwise
to (chloromethyl)trichlorosilane (36.78 g, 200 mmol) in
ether (50 ml) at room temperature. The mixture was
refluxed for 4.5 h, magnesium salts were filtered and
washed with anhydrous ether and benzene. Removal of
the solvents by rotary evaporation followed by vacuum dis-
tillation gave a crude product (23.04 g, b.p. 104–110 ꢁC/
6 mm Hg) containing Ph(ClCH2)SiCl2 (by NMR, 96%,
22.04 g, 97 mmol, 49% yield). Lit. [42]: b.p. 110–118 ꢁC/
3.3.2. Phenyl(chloromethyl)dihydrosilane
The compound (4.10 g, 26.3 mmol, 56% yield) was
obtained from Ph(ClCH2)SiCl2 (9.54 g, 42.3 mmol) as a
1
clear, colorless liquid, b.p. 71–73 ꢁC/6 mm Hg. H NMR
3
(CDCl3): d 3.12 (t, 2H, SiCH2Cl, J = 3.32 Hz), 4.54 (t,
2H, SiH, 1J(SiH) = 206.08 Hz), 7.40 (m, 2H, Hm), 7.46
(m, 1H, Hp), 7.64 (m, 2H, Ho). 13C NMR (CDCl3): d
25.09 (SiCH2Cl), 128.31 (Cm), 129.50 (Ci), 130.57 (Cp),
135.55 (Co). 29Si NMR (CDCl3): dꢀ31.85. Anal. Found:
C, 53.98; H, 5.88; Si, 17.09. Calc. for C7H9ClSi: C, 53.66;
H, 5.79; Si, 17.93%.
1
12 mm Hg. H NMR (CDCl3): d 3.32 (s, 2H, SiCH2Cl),
7.48 (m, 2H, Hm), 7.56 (m, 1H, Hp), 7.78 (m, 2H, Ho).
29Si NMR (CDCl3): d 7.15.
Crude product was used without further purification for
preparation of Ph(ClCH2)SiH2.
3.3.3. Benzyl(chloromethyl)dihydrosilane
This compound was prepared from Bn(ClCH2)SiCl2
(2.41 g, 10 mmol) in 62% yield (1.06 g, 62.3 mmol). Color-
1
3.2.3. Benzyl(chloromethyl)dichlorosilane
The compound was prepared according to a modified
literature procedure [41,43].
less liquid, b.p. 73–74 ꢁC/3 mm Hg. H NMR (CDCl3): d
3
2.45 (t, 2H, CH2Ph, J = 3.42 Hz), 2.91 (t, 2H, SiCH2Cl,
1
3J = 2.69 Hz), 4.08 (tt, 2H, SiH, J(SiH) = 203.2 Hz), 7.17
The Grignard reagent prepared from benzyl chloride
(30.80 g, 197 mmol) and magnesium powder (4.80 g) in
anhydrous Et2O (150 ml) was added to (chloromethyl)tri-
chlorosilane (29.00 g, 157 mmol) in ether (70 ml). The mix-
ture was refluxed for 4.5 h, cooled, filtered, and fractionally
distilled to give Bn(ClCH2)SiCl2 (18.87 g, 83 mmol, 42%
yield), b.p. 102–106 ꢁC/1 mm Hg. 1H NMR (CDCl3): d
2.90 (s, 2H, CH2Ph), 3.11 (s, 2H, SiCH2Cl), 7.38 (m, 2H,
Hm), 7.29 (m, 3H, Ho, Hp). 13C NMR (CDCl3): d 6.84
(CH2Ph), 28.83 (SiCH2Cl), 126.27 (Cp), 128.87 (Co),
129.06 (Cm), 133.03 (Ci). 29Si NMR (CDCl3): d 6.22. Anal.
Found: C, 41.64; H, 3.81; Si, 11.52. Calc. for C8H9Cl3Si: C,
40.10; H, 3.79; Si, 11.72%.
(m, 2H, Ho), 7.18 (m, 1H, Hp), 7.30 (m, 2H, Hm) 13C
NMR (CDCl3): d 16.89 (CH2Ph), 23.58 (SiCH2Cl), 124.67
(Cp), 127.78 (Co), 128.32 (Cm), 137.73 (Ci). 29Si NMR
(CDCl3): dꢀ28.15. Anal. Found: C, 55.89; H, 6.54; Si,
16.25. Calc. for C8H11ClSi: C, 56.28; H, 6.49; Si, 16.45%.
3.4. Preparation of
organyl(chloromethyl)hydrochlorosilanes
3.4.1. General procedure:
Methyl(chloromethyl)hydrochlorosilane (2)
N-chlorosuccinimide (13.35 g, 100 mmol) was added to
a solution of Me(ClCH2)SiH2 (9.39 g, 100 mmol) in

V.A. Pestunovich et al. / Journal of Organometallic Chemistry 692 (2007) 2160–2167
2165
1
CH2Cl2 (20 ml) at 0 ꢁC over a period of 1 h, and the result-
ing mixture was allowed to warm gradually to room tem-
perature and stirred for 1.5 h. After the precipitate was
filtered, the residue was fractionally distilled to give 2
(8.37 g, 65 mmol, 65% yield) as a colorless liquid, b.p. 94-
m.p. 53–54 ꢁC (dec.). H NMR (CDCl3): d 0.64 (d, 3H,
3
MeSi, J = 1.83 Hz), 1.87-1.91 (m, 4H, CH2-4,5), 2.46 (m,
2H, CH2-3), 2.74, 2.80 (dd, 2H, NCH2Si, J = 16.16 Hz,
2
3J = 5.48 Hz), 3.42 (t, 2H, CH2-6, 3J = 5.42 Hz), 5.23
(dq, 1H, SiH, J(SiH) = 286.44 Hz). 13C NMR (CDCl3): d
6.01 (MeSi), 19.48 (C-4), 19.64 (C-5), 27.76 (C-3), 41.43
(NCH2Si), 48.76 (C-6), 173.70 (NCO). Anal Found: C,
43.56; H, 7.29; N, 7.39. Calc. for C7H14ClNOSi: C, 43.85;
H, 7.36; N, 7.31%.
1
95ꢁC, n2D0 1.4415. Lit. [46] b.p. 95–97 ꢁC, n2D0 1.4395. H
NMR (CDCl3): 0.65 (d, 3H, MeSi, 3J = 3.1 Hz), 3.00,
3.08 (dd, 2H, SiCH2Cl, 2J = 13.83 Hz, 3J = 4.40 Hz,
3J = 1.28 Hz), 4.86–4.90 (dqd, 1H, SiH, J(SiH) =
234.72 Hz). 13C NMR (CDCl3): dꢀ2.06 (MeSi), ꢀ28.50
(SiCH2Cl).
3.5.2. N-(phenylhydrochlorosilylmethyl)piperidone-2 (6)
A mixture of chelates (6) and (7) (0.262 g, 87%, 4.5:1
ratio) was obtained from (3) (0.204 g, 11.9 mmol) and
(1).
Data for (6). White crystals, m.p. 89–92 ꢁC. H NMR
(CDCl3): d 1.78 (m, 4H, CH2-4,5), 2.42 (tt, 2H, CH2-3,
Preparation of hydrochlorosilanes 3 and 4 was carried
out at room temperature.
1
3.4.2. Phenyl(chloromethyl)hydrochlorosilane (3)
The compound was prepared from Ph(ClCH2)SiH2
(2.00 g, 12.8 mmol) in 81% yield. Colorless oil, b.p. 69–
trans
trans
gemJ ꢁ
J
= 18.5 Hz,
J
ꢁ
cisJ = 6.0 Hz), 2.93,
ax
eq
1
2
71 ꢁC/2 mm Hg. H NMR (CDCl3): d 3.21, 3.24 (dd, 2H,
2.97 (dd, 2H, SiCH2N, JAB = 16.33 Hz, 3J = 5.2 Hz),
3.65 (m, 2H, CH2-6), 5.74 (dd, 1H, SiH, J(SiH) =
298.7 Hz), 7.31 (m, 3H, Hm, Hp), 7.77 (m, 2H, Ho). 13C
NMR (CDCl3): d 18.39 (C-4), 21.44 (C-5), 26.55 (C-3),
39.83 (NCH2Si), 47.56 (C-6), 126.45 (Co), 127.36 (Cp),
133.30 (Cm), 138.89 (Ci), 173.40 (NCO). 15N NMR
(CDCl3): dꢀ245.4. Anal. Found: C, 56.48; H, 6.56. Calc.
for C7H8ClSi: C, 56.79; H, 6.36%.
2
3
3
SiCH2Cl, J = 14.07 Hz, J = 3.32 Hz, J = 2.38 Hz), 5.32
(dd, 1H, SiH, 1J(SiH) = 246.34 Hz), 7.47 (m, 2H, Hm),
7.54 (m, 1H, Hp), 7.73 (m, 2H, Ho). 13C NMR (CDCl3):
d 27.72 (SiCH2Cl), 128.36 (Cm), 129.12 (Ci), 131.33 (Cp),
133.86 (Co). Anal. Found: C, 44.76; H, 4.36; Si, 14.42. Calc.
for C7H8ClSi: C, 43.99; H, 4.22; Si, 14.69%.
3.4.3. Benzyl(chloromethyl)hydrochlorosilane (4)
This compound was obtained from the corresponding
dihydrosilane (1.34 g, 7.8 mmol) in 49% yield (0.78 g). Col-
3.5.3. O-(phenylhydrochlorosilylmethyl)piperidone-2 (7)
1
Data for (7). H NMR (CDCl3): d 1.77 (m, 4H, CH2-
1
orless oil, b.p. 88–89 ꢁC/3 mm Hg. H NMR (CDCl3): d
4,5), 2.44 (m, 2H, CH2-3), 4.08, 4.11 (dd, 2H, SiCH2O,
2
3
2.60, 2.61 (AB quartet, 2H, CH2Ph, JAB = 14.18 Hz;
2J = 15.58 Hz, J = 2.42 Hz), 3.23 (m, CH2-6), 5.68 (dd,
2
3J = 2.2 Hz), 2.90, 2.95 (dd, 2H, SiCH2Cl, J = 13.94 Hz,
1H, SiH, J(SiH) = 286.9 Hz), 7.32 (m, 3H, Hm, Hp), 7.60
(m, 2H, Ho). 13C NMR (CDCl3): d 17.73 (C-4), 20.36 (C-
5), 24.34 (C-3), 57.92 (SiCH2O), 40.43 (C-6), 126.91 (Co),
127.36 (Cp), 132.12 (Cm), 138.13 (Ci), 172.40 (NCO). 15N
NMR (CDCl3): dꢀ191.8.
3J = 1.22 Hz, 3J = 3.67 Hz), 4.85 (dtd, 1H, SiH,
3
J(SiH) = 243.1 Hz), 7.14 (d, 2H, Ho, J = 6.85 Hz), 7.16
3
(t, 1H, Hp, J = 7.09 Hz), 7.26 (dd, 2H, Hm). 13C NMR
(CDCl3): d 22.93 (CH2Ph), 26.67 (SiCH2Cl), 125.85 (Cp),
128.80 (Co), 128.91 (Cm), 134.80 (Ci). 29Si NMR (CDCl3):
1
d 1.60. H NMR (C6D6): d 2.18, 2.20 (AB quartet, 2H,
3.5.4. N-(benzylhydrochlorosilylmethyl)piperidone-2 (8)
The compound was obtained from (4) (0.105 g,
0.51 mmol) in 87% yield as colorless crystals, m.p. 59–
2
CH2Ph, JAB = 14.43 Hz; 3J = 2.2 Hz) 2.38 (d, 2H,
SiCH2Cl, 3J = 2.69 Hz), 4.65 (tt, 1H, SiH,
3
1
J(SiH) = 242.33 Hz), 6.91 (d, 2H, Ho, J = 7.58 Hz), 6.96
61 ꢁC. H NMR (C6D6): 0.71 (m, 2H, CH2-4), 0.77 (m,
(t, 1H, Hp, 3J = 7.34 Hz), 7.06 (t, 2H, Hm). 13C NMR
(CDCl3): d 22.08 (CH2Ph), 25.71 (SiCH2Cl), 125.18 (Cp),
128.15 (Co), 128.24 (Cm), 134.21 (Ci). 29Si NMR (CDCl3):
d 3.31. Anal. Found: Si, 13.76; Cl, 34.33. Calc. for
C8H10Cl2Si: Si, 13.69; Cl, 34.56%.
2H, CH2-5), 1.61 (m, 2H, CH2-3), 1.96, 2.11 (m, 2H,
CH2-6), 2.16, 2.51 (dd, 2H, CH2Ph, 2J = 16.63 Hz;
3J = 5.4 Hz), 2.86, 3.05 (AB quartet, 2H, SiCH2N,
2J = 12.72 Hz), 6.10 (d, 1H, SiH, J(SiH) = 295.2 Hz),
7.00 (m, 1H, Hp), 7.11 (m, 2H, Hm), 7.31 (m, 2H, Ho).
13C NMR (CDCl3): d 19.15 (C-4), 21.39 (C-5), 27.17 (C-
3), 31.97 (CH2Ph), 39.99 (SiCH2N), 47.56 (C-6), 124.52
(Cp, C6H5CH2), 129.07 (Co, C6H5CH2), 129.57 (Cm,
C6H5CH2), 140.19 (Ci, C6H5CH2), 173.07 (NCO). 29Si
3.5. Reactions of organyl(chloromethyl)hydrochlorosilanes
with N-trimethylsilylpiperidone-2 (1)
1
3.5.1. General procedure: Preparation of N-
(methylhydrochlorosilylmethyl)piperidone-2 (5)
NMR (CDCl3): dꢀ66.36. H NMR (CDCl3): d 1.55 (m,
2H, CH2-4), 1.69 (m, 2H, CH2-5), 2.29 (m, 2H, CH2-3),
2.81, 3.11 (m, 2H, CH2-6), 2.59, 2.66 (AB quartet, 2H,
SiCH2N, 2J = 12.41 Hz), 2.16, 2.26 (AB quartet, 2H,
CH2Ph, 2J = 12.81 Hz), 5.42 (d, 1H, SiH, J(SiH)
=298.6 Hz), 7.06 (m, 1H, Hp), 7.14 (m, 2H, Ho), 7.19 (m,
2H, Hm). Anal. Found: Si, 10.84; N, 5.51. Calc. for
C13H18ClSiNO: Si, 10.49; N, 5.23%.
A solution of (2) (1.29 g, 10 mmol) in hexane (10 ml)
was added to a solution of (1) (1.71 g, 10 mmol) in hexane
(15 ml) at room temperature. The resulting white suspen-
sion was stirred for 1 h. The solvent was decanted off and
the residue was washed with hexane (2 · 5 ml) and dried
under vacuum to yield (5) (1.14 g, 60%) as a white crystals,

2166
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3
3
3.6. Synthesis isopropoxysilanes
2J = 15.2 Hz, J = 4.4 Hz), 3.30 (t, 2H, CH2-6, J = 5.24
Hz), 3.92 (hept, 1H, CHO), 4.72 (narrow m, 1H, SiH,
J(SiH) = 235 Hz). 29Si NMR (CDCl3): dꢀ15.51.
3.6.1. Methyl(chloromethyl)isopropoxychlorosilane (11)
This compound was prepared from Me(ClCH2)SiCl2
according to [36]. Physical data and 1H NMR data are con-
sistent with reported in [36]. 13C NMR (CDCl3): d 0.82
(MeSi), 25.16 (Me2CH), 29.25 (SiCH2Cl), 67.55 (CHO).
29Si NMR (CDCl3): dꢀ1.09.
Acknowledgment
Financial support from INTAS (Grant No. 03-51-4164)
is gratefully acknowledged.
3.6.2. N-(methylisopropoxychlorosilylmethyl)piperidone-2
(12)
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A solution of (1) (0.22 g, 1.33 mmol) in hexane (1 ml)
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withdrawn by means of a syringe. Removal of the solvent
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48.66 (C-6), 65.75 (CHO), 172.65 (NCO). 29Si NMR
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3.6.3. Methyl(chloromethyl)isopropoxysilane (13)
A solution of i-PrOH (0.6 g, 10 mmol) in hexane (1 ml)
was added to a mixture of (2) (1.30 g, 10 mmol), urea
(0.61 g, 10 mmol), and hexane (3 ml), and the resulting
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3
d 0.34 (d, 3H, MeSi, J = 2.72 Hz), 1.22 (d, 6H, Me2CH,
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3
2J = 14.51 Hz, J = 2.42 Hz), 4.12 (hept, 1H, CHO), 4.68
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(CHO). 29Si NMR (CDCl3): dꢀ4.57. Anal. Found: C,
39.24; H, 8.60, Si, 18.34. Calc. for C5H13ClOSi: C, 39.33;
H, 8.58; Si, 18.39%.
3.6.4. N-(methylisopropoxysilylmethyl)piperidone-2 (14)
To the solution of (2) (1.311 g, 9.2 mmol) in heptane (3
ml) was added a solution of (1) (1.575 g, 9.2 mmol) in hep-
tane (3 ml). The reaction mixture was stirred for 1.5 h at
room temperature. The volatile compounds were removed
under vacuum. To the residue was added heptane (5 ml)
and a solution of isopropanol (0.553 g, 9.2 mmol) and tri-
ethylamine (0.937 g, 9.2 mmol) in heptane (5 ml) at 0 ꢁC.
The reaction mixture was stirred for 30 min at 0 ꢁC and
the resulting ammonium salts were filtered. Evaporation
of the solvent and volatile products under reduced pressure
(1 mm Hg) gave crude product (0.787 g) as a colorless vis-
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3
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