Scheme of hydrolysis of five-coordinate chlorosilanes by X-ray diffraction data

Article abstract of DOI:10.1134/S1070363211120048

Hydrolysis of monochelate five-coordinate chlorosilanes MeC(O)N(Me)CH ₂SiMe₂Cl (Ia), L₇CH₂SiMe ₂Cl (Ib), L₈CH₂SiMe₂Cl (Ic), PhtImCH₂SiMe₂Cl (Id), MeC(O)N(Me)CH₂SiMePhCl (IIa), and Im₅CH₂SiMePhCl (IIe), containing a monoanionic C,O-chelating ligand LCH₂ [L is an amide, n-membered lactam (L ⁿ), imide (Imⁿ), or phthalimide (PhtIm) residue]. The structures of the starting chlorides and their hydrolysis products were established by means of X-ray diffraction analysis. Based on experimental and published data, a general scheme of hydrolysis of mono-C,O-chelate chlorosilanes was suggested, including initial formation of silyloxonium chlorides III and subsequent formation of disiloxane dihydrochlorides IV. Pleiades Publishing, Ltd., 2011.

Full text of DOI:10.1134/S1070363211120048

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 12, pp. 2428–2439. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.G. Shipov, E.P. Kramarova, T.P. Murasheva, A.A. Korlyukov, S.A. Pogozhikh, S.A. Tarasenko, V.V. Negrebetskii, I.P. Yakovlev,
Yu.I. Baukov, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 12, pp. 1979–1990.
Scheme of Hydrolysis of Five-Coordinate Chlorosilanes
by X-Ray Diffraction Data
A. G. Shipova, E. P. Kramarovaa, T. P. Murashevaa, A. A. Korlyukovb, S. A. Pogozhikhb,
S. A. Tarasenkoa, V. V. Negrebetskiia, I. P. Yakovlevc, and Yu. I. Baukova
a Russian State Medical University, ul. Ostrovityanova 1, Moscow, 117997 Russia,
e-mail: baukov@rgmu.ru
b Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia
c Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
Received July 7, 2011
Abstract—Hydrolysis of monochelate five-coordinate chlorosilanes MeC(O)N(Me)CH2SiMe2Cl (Iа),
L7CH2SiMe2Cl (Ib), L8CH2SiMe2Cl (Ic), PhtImCH2SiMe2Cl (Id), MeC(O)N(Me)CH2SiMePhCl (IIа), and
Im5CH2SiMePhCl (IIe), containing a monoanionic С,О-chelating ligand LCH2 [L is an amide, n-membered
lactam (Ln), imide (Imn), or phthalimide (PhtIm) residue]. The structures of the starting chlorides and their
hydrolysis products were established by means of X-ray diffraction analysis. Based on experimental and
published data, a general scheme of hydrolysis of mono-С,О-chelate chlorosilanes was suggested, including
initial formation of silyloxonium chlorides III and subsequent formation of disiloxane dihydrochlorides IV.
DOI: 10.1134/S1070363211120048
Typical representatives of silicon compounds with
nonstandard coordination, specifically neutral mono-
chelate five-coordinate monochlorosilanes containing
monoanionic amidomethyl and related С,О-chelating
ligands (LCH2), have been studied in sufficient detail
[1–3]. Effective synthetic approaches to such
compounds [2, 4–6] and, on their basis, to other five-
coordinate silicon derivatives with widely varied O→Si
coordination bond strength have been developed [1–3,
6–8]. This made it possible to gain insight into the
structural features of compounds with a SiC3OX
coordination entity (X = Hlg, OAlk, OAr, 0.5O, OTf)
[7–11] and their stereodynamic behavior [12, 13], as
well as to use them as models for studying the
hypervalence problem [2, 14] and SN reactions at the
silicon atom [1–3, 10, 11, 15–18].
coordinate Si atom in the polymeric chain [21]. Novel
Si-substituted N-(dimethylsilyl)- and N-(methylphenyl-
silylmethyl)amides and -lactams with a SiC3OX coordina-
tion entity (X = Hlg, OTf) and a chiral carbon atom in
the amide or lactam fragment have been synthesized,
and their stereodynamic behavior has been studied [13].
At the same time, one of the most important reac-
tions of mono-С,О-chelate chlorosilanes, viz. hyd-
rolysis, have still scarcely been studied. Note that the
hydrolysis process can be complicated due to the
ability of the donor oxygen atom for additional coordina-
tion. In the present paper we describe hydrolysis
products of first synthesized and known С,О-chelate
chlorosilanes LCH2Si(R)MeCl I and II with a SiC3OCl
coordination entity in the absence and in the presence
of HCl acceptors. Based on the X-ray diffraction and
NMR data for the intermediate reaction products:
silyloxonium chlorides [LCH2Si(R)MeOH2]Cl III and
disiloxane dihydrochlorides [LCH2Si(R)Me]2O·2HCl
IV, as well as the final hydrolysis products: disil-
oxanes [LCH2Si(R)Me]2O V and VI, a general scheme
of hydrolysis of five-coordinate chlorosilanes I and II
[here and hereinafter, R = Me (I, III–V), Ph (II, VI)]
is considered.
However, active research in this field has been con-
tinued. For example, five-coordinate [(2-oxopiperidin-
1-yl)methyl]-R-hydrochlorosilanes (R = Me, Ph, Bn)
have been synthesized [19]. Cationic polymerization
with silacycle opening in sila[1]ferrocenophane [20] in
the presence of a salt containing a silylium cation
[MeC(O)NCH2SiMe2]+B[(3,5-CF3)2C6H3]4–, has been
used to prepare a poly(ferrocenylsilane) with a five-
2428

SCHEME OF HYDROLYSIS OF FIVE-COORDINATE CHLOROSILANES
2429
Mono-С,О-chelate chlorosilanes I and II and
their final hydrolysis products disiloxanes V and
VI. As objects for hydrolysis study we chose five-
coordinate monochelate complexes of the general
formula LCH2Si(R)MeCl [R = Me (I), Ph (II)],
specifically chlorides MeC(O)N(Me)CH2SiMe2Cl (Iа),
L7CH2SiMe2Cl (Ib), L8CH2SiMe2Cl (Ic), PhtImCH2·
SiMe2Cl (Id), MeC(O)N(Me)CH2SiMePhCl (IIа), and
Im5CH2SiMePhCl (IIe), which contain a monoanionic
amidomethyl or related С,О-chelating ligand LCH2
[L is an amide, n-membered lactam (Ln), imide (Imn),
or phthalimide (PhtIm) residue].
The previously described chlorides Iа [4], Ib [6],
and IIа [13] were prepared by a common procedure
for neutral monochelate five-coordinate silicon com-
plexes, i.e. by the reaction of trimethylsilyl derivatives
of the corresponding amides, lactams, and imides
L–SiMe3 with ClCH2SiMe2Cl or ClCH2SiMePhCl [reac-
tion (1), route a]. The reactions were performed under
thermodynamic control, and only final N-silylmethyla-
tion products I and II were isolated (a more detailed
scheme is given in [19]).
b, H2O
a, ClCH2Si(R)MeCl
(1)
[LCH2Si(R)Me]2O,
LCH2Si(R)MeCl
Ia_Ic, IIa, IIe
L
SiMe3
_Me3SiCl
(NaHCO3)
Va, Vc, Vd, VIa, VIe
R = Me, L = MeC(O)N(Me) (а), L7 (b), L8 (c), PhtIm (d); R = Ph, L = Im5 (e).
In a similar was we synthesized chloride Ic, the first
representative of five-coordinate monochelate com-
plexes containing an eight-membered lactam (enanto-
lactam) fragment incorporated into a chelate ligand, as
well as chloride IIe (yields 87 and 95%, respectively).
Disiloxane Vс was, too, prepared by hydrolysis of
siloxonium chloride IIIс in the presence of ammonium
carbonate.
Products of incomplete hydrolysis of chlorides I.
A characteristic feature of five-coordinate silicon com-
pounds [1, 3], including those containing Si–Cl bonds
[23], is that they exhibit enhanced reactivity compared
with four-coordinate Si atom. Therefore, it is not
surprising that chlorosilanes I and II are easily hyd-
rolyzed and not infrequently are quite sensitive to
atmospheric moisture.
The reaction of ClCH2SiMe2Cl with N-SiMe3-
phthalimide gave, against expectations, no chloride Ie.
A substance isolated in 43% yield was identified as its
hydrolysis product disiloxane Vd. In an analogous
experiment in the presence of a base (NaHCO3) the
yield of disiloxane Vd was 50.5%. Chloride Id could
not also be prepared by a method of silylation of
imides we described previously: reaction of phthal-
imide with ClCH2SiMe2Cl and hexamethyldisilazane.
Instead of the target chloride Ic we isolated N-(di-
methylphthalimidosilylmethyl)phthalimide (VII) [22].
It can be stated with assurance that the structure of
two types of intermediate hydrolysis products of
mono-С,О-chelate chlorosilanes LCH2SiMe2Cl I:silyl-
oxonium chlorides [LCH2SiMe2OH2]Cl III [24] and
disiloxane dihydrohydrochlorides (LCH2SiMe2)2O·
2HCl IV [25], was reliably established by X-ray
diffraction. Five-coordinate silanols LCH2SiMe2OH
can also be considered as intermediates. The formation
of their analogs: hydrosilanol L6CH2SiMe(H)OH and
chlorosilanol L6CH2SiMe(OH)Cl, as primary hyd-
rolysis products of chlorosilane L6CH2Si(H)MeCl
(VIII) was suggested on the basis of 1H and 29Si NMR
spectra [19]. These products were detected in a
fraction of ~10% in the NMR spectrum of chlorosilane
VIII, which was explaned by the presence of traces of
water in the solvent (CDCl3).
The pentacoordination of silicon in chloride Ib was
established by X-ray diffraction analysis in our
previous work [10] and in chlorides Iа, Ic, and IIа, in
the present work.
Attempted recrystallization of chloride IIe (a hot
benzene solution was poured into hexane) gave
crystals of its hydrolysis product disiloxane (Im5CH2·
SiMePh)2O (VIe). The structure of the latter was con-
firmed by X-ray diffraction analysis.
The previously unknown final hydrolysis products
of chlorides Iа, Ic, IIа, and IIe, specifically di-
siloxanes Vа, Vc, VIа, VIe, were prepared in high
yields by treatment of the starting chlorides with water
in the presence of NaHCO3 [reaction (1), route b].
By X-ray diffraction we established the structure of
a five-coordinate silicon compound on the basis of
quite a ridig tetradentate ligand, substituted 1-aqua-5-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 12 2011

2430
SHIPOV et al.
carbasilatrane (IX), obtained by hydrolysis of its
C2H5OH analog [26]. Nevertheless, the possibility of
detection of five-coordinate intermediates in which a
molecule of water is coordinated with silicon, namely
neutral aqua complexes like LCH2SiMe2OH2, seems
very unlikely in our case.
Ph
H
C
O
N
O
Cl_
Me
Si OH2
CH2
Si
C
t-Bu
Me
H
3
O
+
H
IХ
Х
The Cambridge Structural Database [27] contains
data for two silyloxonium chlorides X [24, 28] and XI
[29]. Furthermore, the structure of bromide [PhC(O)
NHCH2SiMe2OH2]Br, a Br analog of compound X,
was established [24, 28]. An urea derivative, silyloxo-
nium chloride XII, was synthesized and structurally
characterized [30].
When the starting chloride Iс was prepared in
hexane and then crystallized from the same solvent, we
obtained, according to the elemental analysis, hydro-
chloride IIIc. If benzene was used as a solvent, the
isolated product was assigned, by X-ray diffraction and
elemental analysis data, the structure of solvate
IIIc·H2O.
Me
In the present work we also prepared different-type
intermediate hydrolysis products of mono-С,О-chelate
chlorosilanes, namely disiloxane dihydrochlorides
[LCH2SiMe2]2O·2HCl IV. Thus, dihydrochlorides IVа
and IVb were isolated, after hydrolysis of chlorides Iа
and Ib in air in the absence of bases (benzene solutions
of chlorides Iа and Ib were left in air at room
temperature until the solvent evaporated almost
completely).
Me
H
H
+
O
Si
O
Cl_
C
N
ХI
HN
N
Thus, disiloxanes function as bases binding HCl in
reaction (3). The structure of dihydrochloride IVа was
established by X-ray diffraction.
Cl_
H
+
O
Si
O
H
Me
Me
ХII
R1
R2
C
In the present work we determined an X-ray
diffraction structure of one more representative of this
quite a rare class of compounds, silyloxonium chloride
[L8CH2SiMe2OH2]Cl (IIIc). It was isolated as a
hydrate IIIc·H2O upon recrystallization of chloride Ic
without special protection from atmospheric moisture.
N
O
Me
Me
2
H2C
Si
Cl
Iа, Ib
Me
Me
(CH2)4
H
(CH2)4
Si
Cl
O
H2O
O
C
C
O
N
O
N
CH2
H2O
(3)
Me
Me
Me
R1
(2)
N
CH2
CH2
Si
Cl
Si
R2
Me
H
2
O
IVa, IVb
+
H
IIIc
Cl_
R1 = R2 = Me (а); R1 = R2 = (CH2)5 (b).
Ic
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SCHEME OF HYDROLYSIS OF FIVE-COORDINATE CHLOROSILANES
2431
Note that adducts of disiloxanes with С,О-chelating
ligands have been described. In particular, the X-ray
diffraction structures of adduct (L5CH2SiMe2)2O·
2CCl3COOH (XIII) synthesized from the correspond-
ing disiloxane and CCl3COOH [31], as well as of
dihydrochloride (L5CH2SiMe2)2O·2HCl (XIV) were
established, even though the synthesis of the latter
compound was not reported [25]. Thus, our described
dihydrochlorides IVа and IVb are the first compounds
of this type prepared by hydrolysis of five-coordinate
mono-С,О-chelate chlorosilanes.
reaction of hydrosilane PhSiHMe2 with CF3SO3H gave
triflate Me2Si(H)OTf in a 86% isolated yield [33].
The composition and structure of previously
unknown five-coordinate monochelates I–III and four-
coordinate disiloxane dihydrochlorides and disiloxanes
IV–VI were established by means of elemental
analysis and IR and NMR spectroscopy; the structure
of compounds Iа, Ic, IIа, IIIc, IVа, Vd, and VIe was
confirmed by X-ray diffraction analysis.
IR spectroscopy. Like with earlier described
mono-С,О-chelate chlorosilanes, specifically amide
and lactam derivatives [5, 6], including chlorides Iа
[4], Ib [6], and IIа [13] used in the hydrolysis study,
the IR spectrum of chloride Iс contains in the range
1700–1400 cm−1 two absorption bands of associated
stretching vibrations ν(С=О) and ν(С=N) which relate
It should be added that the protonation of an amide
rather than disiloxane oxygen was observed in adducts
of 2,6-disilamorpholines XV with HCl (XV·HCl), and
CF3COOH (XV·CF3COOH) [32]. The structure of the
latter adduct was confirmed by X-ray diffraction.
Me
··· ···
to the N—C—O fragment of the chelate ligand (a
strong band at 1600 cm−1 and a medium band at
1510 cm−1). These observables provide evidence show-
ing that the Si atom in chloride Iс is five-coordinate
due to O→Si coordination.
R
O
Me
Si
O
Si
C
N
X
H
Me
Me
At the same time, in the derivative of a five-mem-
bered imide, chloride IIe, the coordination interaction
O→Si in solution may well be lacking. Stretching
vibrations of the carbonyl groups in IIe appear as
bands peaking at 1775 [νs(C=O)] and 1700 cm−1
[νas(C=O)]. Their positions are close to those in the
spectrum of the ClMe2 analog Im5CH2SiMe2Cl (1750
and 1690 cm−1 [34]). These absorption bands are
appreciably shifted to high frequencies compared to
those of the six-membered imide derivative Im6CH2·
SiMe2Cl (1717 and 1670 cm−1), where a fairly weak
but reliably detected O→Si coordination takes place
[34].
ХV НХ
XV·HX, R = Me, X = Cl, CF3COO; R = ClCH2, X = CF3SO3.
In the case of imidomethylchlorosilanes Id (in situ)
and IIe, compounds in which the O→Si intramolecular
interaction is almost lacking (see below), no inter-
mediate hydrolysis products could be obtained. As
mentioned above, after hydrolysis of these compounds
at ~50–60°С by moisture contained in air or solvent,
we isolated as final productsdisiloxanes Vd and VIe,
respectively, rather than compounds III or IV.
Thus, the reduced donor ability of the oxygen atom
in the imide derivatives studied compared with their
amide and lactam analogs, leads, on the one hand, to
the lack of O→Si coordination in their molecules and,
on the other, excludes their involvement as acceptors
of HCl formed on hydrolysis.
Evidence for the five-coordinate state of silicon in
silanol hydrochloride IIIс due to O→Si coordination
comes from the IR spectrum which contains in the
range 1700–1400 cm−1, like with chlorosilanes I, two
··· ···
absorption bands of the N—C—O fragment of the
chelate ligand (1580 and 1510 cm−1), similar to those
observed previously in silyloxonium chloride X [24,
28]. Note also quite a broad strong absorption at 3200–
2900 cm–1 with maxima about 3040 and 2980 cm–1,
associated with intermolecular Н-bonds involving Cl
atoms.
No intermediate hydrolysis products could also be
obtained in the case of chloride IIа, which
differentiates them from chloride Iа containing a Ph
group on silicon. Chloride IIa is not hydrolyzed at
room temperature in the absence of a base; under more
rigid conditions (long-term boiling with water), Si–C
(Ph) bond cleavage takes place. Such cleavage under
the action of strong acids is characteristic of four-
coordinate silicon compounds. For example, the
A similar broad strong absorption band at 3200–
3100 cm–1 with its maximum about 3160 cm–1 is
observed in disiloxane dihydrochlorides IVa and IVb
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 12 2011

2432
SHIPOV et al.
points to the lack of any appreciable O→Si coordina-
tion in IIe in solutions.
29
The Si NMR signals of dihydrochlorides IVа and
IVb and disiloxanes Vа–Vd are observed at δSi –3.5 to
15 ppm, which corresponds to their position in
ordinary siloxanes {for example, the δSi of (Me3Si)2O
is 7.4 ppm [12]}, providing evidence for the four-coor-
dinate state of silicon in these compounds in solution.
Note that the silicon signal of adduct XV·HCl
protonated by the amide oxygen was observed at
10.7 ppm [32].
X-ray diffraction study. The geometry of the
coordination entity of Si in the three neutral five-
coordinate С,О-chelate chlorosilanes Ia, Ic, and IIa
(Table 1, Figs. 1 and 2) is a distorted trigonal
bipyramid with the Si atom deviating from the equa-
torial plane by 0.026–0.068 Å towards Cl. The replace-
ment of the methyl group on silicon by phenyl in going
from compound Ia to IIa does not affect essentially
the Si–O coordination bond length. Therewith, the Si–
Cl bond gets longer by 0.03 Å, which can be explained
by repulsion between the phenyl substituent and
chlorine atom (the CSiCl angle in IIa is larger by ~2°
than the respective angle in Ia).
Fig. 1. General view of a molecule of chloride Iа in crystal
(2 independent molecules) (H atoms are not shown).
(О–Н stretching vibrations perturbed by intermolecular
Н-bonding). However, in these cases we observed in
the carbonyl stretching vibration region a single strong
band at 1600 and 1640 cm–1, respectively (protonated
carbonyl), which implies lacking O→Si intramolecular
interaction.
Like with chloride IIe, the IR spectra of imido-
methyl-substituted disiloxanes Vd and VIe show two
carbonyl absorption bands (1765–1780 and 1685–
1680 cm−1), whose position implies lacking O→Si
coordination. Such bonding is also lacking in di-
siloxanes Vа and Vc: Their spectra contain a single
strong absorption band at 1630–1615 cm−1 [ν(C=O)]
{compare with the position of this band (1635 cm−1) in
a seven-membered lactam derivative (L7CH2SiMe2)2O
[8]}. Therewith, no additional absorption at 1600–
1500 cm−1, characteristic of С,О-chelate ligand LCH2,
is observed.
More appreciable are differences between com-
plexes Ia and Ic. Replacement of methyl substituents
by a more donor eight-membered lactam ring results in
strengthening of the Si–O bond and weakening of the
Si–Cl bond (the corresponding distances have changed
by 0.03 and 0.04 Å). The bulky substituent in complex
Ic disturbs planarity of the chelate ring. The chelate
rings in complexes Ia and IIa are in fact planar,
whereas that in compound Iс is an envelope with the Si
atom deviating by 0.1003(6) Å.
1
NMR spectroscopy. The H, 13C, and 29Si NMR
spectra of compounds I–VI are consistent with the
suggested structures. As known, the NMR spectra of
five-coordinate silicon compounds differ from those of
model four-coordinate derivatives by enhanced 29Si
shielding [1, 2, 12]. For our studied chlorides Iа–Ic
and IIа and most known mono-С,О-chelate mono-
chlorosilanes like I, an upfield shift of the 29Si NMR
signal (δSi from –32 to –54 ppm) compared to their
closest tetrahedral analog ClCH2SiMe2Cl (23.7 ppm)
[35] suggests quite a strong O→Si coordination bond
in these compounds in the liquid phase [1, 2, 12, 13].
The structure of the coordination polyhedron of the
Si atom in the hydrolytic intermediate of chloride Ic,
silyloxonium chloride IIIc (Fig. 3), is slightly different
from that in complex Ic. Replacement of Cl by H2O
slightly changes the ΔSi value [from 0.0261(6) to
0.0158(4) Å]. The axial Si1–O1 and Si1–O2 bond orders
are almost equal to each other [the corresponding inter-
atomic distances are 1.9129(15) and 1.9140(16) Å].
The chlorine atom resides in the outer sphere with
respect to Si and does not form interatomic contacts
with it (the shortest Si···Cl distance is 4.084 Å).
The signals of chloride Im5CH2SiMePhCl (IIe) and
its Me2Si analog Im5CH2SiMe2Cl [34] in the 29Si NMR
spectrum in СDCl3 (δSi 15.2 and 25.4 ppm, respec-
tively) are close to those of ClCH2SiMe2Cl [35], which
The cation and anion in silyloxonium chloride IIIc
are associated by O–H···Cl hydrogen bonds. Further-
more, the crystal of IIIc contains an uncoordinated
water molecule which, too, forms hydrogen bonds with
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SCHEME OF HYDROLYSIS OF FIVE-COORDINATE CHLOROSILANES
2433
Fig. 3. General view of a molecule of silyloxonium
chloride hydrate IIIc·H2O in crystal (H atoms of water
molecules are only shown). Principal bond lengths (Å) and
bond angles (deg): Si1–O1 1.9129(15), Si1–O2 1.9140(16),
O1–C4 1.285(2), Si1–C1 1.860(2), Si1–C2 1.855(2), Si1–C3
1.8964(18), O1Si1O2 173.23(6).
Fig. 2. General view of a molecule of chloride IIа in
crystal (H atoms are not shown).
the cation and anion. An analogous structure has been
earlier discussed for two salts with a (benzoylamido)
methyl ligand [24]). The Si1–O2 bonds are longer by
about 0.1 Å than in complex IIIc, whereas the Si1–O1
bond length is almost the same. The latter fact can be
explained by an effect of crystal packing, since both
chloride X and its Br analog [24] contains no
uncoordinated water molecule, which entails consider-
able differences the H-bond systems.
EXPERIMENTAL
The IR spectra of 5% solutions were registered on a
Specord IR-75 instrument in KBr cells. The Н, 13C,
1
19F, and 29Si NMR spectra of СD2Сl2 and CDCl3
solutions were obtained on a Varian XL-400 spectro-
meter (400.1, 100.6, 396, and 79.5 МHz, respectively).
The Н, 13C, and 29Si chemical shifts were measured
1
against internal Me4Si.
Disiloxane dihydrochloride IVа (Fig. 4) can be
considered as one of the possible intermediates of
hydrolysis of chloride Iа, whereas disiloxanes Vd and
VIe as final hydrolysis products of complexes with a
OSiC3Cl coordination entity. Actually, these
complexes contain no endocyclic Si–O coordination
bond (the Si···O interatomic distance is longer than the
sum of the van der Waals radii) (Table 2).
Table 1. Principal geometric parameters (Å, deg) of the Si
coordination entity and the chelate rings in complexes Ia, Ic,
and IIa containing a OSiC3Cl coordination entity
Parameter
Si–Cl
Iа
Ic
IIа
2.309(1)
2.3470(8)
2.3392(13)
Si–O
1.944(2)
1.866(3)
1.888(3)
1.269(4)
1.310(4)
170.79(8)
0.0565(8)
1.9091(16)
1.861(2)
1.897(2)
1.280(2)
1.310(3)
171.68(5)
0.0261(6)
1.939(2)
1.867(4)
1.885 (4)
1.278(4)
1.300(4)
171.02(9)
0.068(1)
а
Si–Ceq
The shortest Si···Cl distance in salt IVa is 4.110 Å,
which points to lacking interaction between these two
atoms. Not being involved in Si···Cl contacts, the
chlorine atom forms O–H···Cl and C–H···Cl hydrogen
bonds with the N-(methylacetamido)methyl fragment
(Table 3). Unlike salt IVa, compounds Vd and VId
(Fig. 5) are not ionic crystals and contain no chlorine
atom and protonated oxygen atom of the amide
fragment. In their structures, weak C–H···O hydrogen
bonds could only be localized.
Si–Cendo
O–C
а
N–Cendo
OSiCl
b
ΔSi
a
Сeq relate to the equatorial carbon atoms and Сendo, to the carobn
atom in the chelate ring. Deviation of the Si atom from the
b
equatorial plane towards Cl.
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2434
SHIPOV et al.
crystallized from a 1:1 ether–hexane mixture, chlorides
Ic, IIа, and silyloxo-nium chloride IIIc, from benzene,
disiloxanes Vd and VIe, from 3:1 and 1:1 hexane–
benzene mixtures, respectively.
Crystal data and details of X-ray diffraction ex-
periments are presented in Table 4. The X-ray
diffraction measurements were performed on a Bruker
Smart 1000 CCD instrument at 120 K. The structures
were solved by the direct method and refined by fill-
matrix least squares on F2 in the anisotropiс approxi-
mation for non-hydrogen atoms. Absorption was
included using SADABS software [41]. The absolute
structure of Iа was established by the Flack parameter
[42], equal to –0.14(8). In disiloxanes IVа, Vd, and
VIe, the independent part is half of the molecule,
whereas the bridging O1 atom occupies a special
position. In the crystal of Iа, there are two independent
molecules. The crystal of Ic contains a solvate benzene
molecule, the lactam ring is disordered in two positions
(С7 and С8), with the occupancies 0.6 and 0.4. The unit
cell of IIIс contains a solvate water molecule.
Fig. 4. General view of the molecule of dihydrochloride
IVа in crystal (Н-bonded hydrogen atoms are only shown).
N-Methyl-N-SiMe3-acetamide
[36],
N-SiMe3-
enantolactam [37], N-SiMe3-succinimide [38], N-
SiMe3-phthalimide [39], chloro(chloromethyl)phenyl-
silane [40], N-(dimethylchlorosilylmethyl)-N-methyl-
acetamide (Iа) [4], N-(dimethylchlorosilylmethyl)-
hexahydroazepin-2-one (Ib) [6], as well as N-methyl-
N-[chloro(methyl)phenylsilylmethyl)acetamide (IIa)
[22] were prepared by known procedures, and their
physicochemical and spectral characteristics were
consistent with published data.
The principal bond lengths and bond angles in the
studied structures are listed in Tables 1 and 2. All
calculations were performed using SHELXTL 5.10
software [43].
Synthesis of N-(dimethylchlorosilylmethyl)-N-
methylacetamide (Iа) and 1,1,3,3-tetramethyl-1,3-
bis(N-methylacetamidomethyl)-1,3-disiloxane dihyd-
rochloride (IVа). а. A mixture of 7 g of N-methyl-N-
SiMe3-acetamide and 7 g of ClCH2SiMe2Cl was
To obtain single crystals for X-ray diffraction
analysis, chloride Iа and dihydrochloride IVа were
Table 2. Principal geometric parameters (Å, deg) of com-
pounds IVа, Vd, and VIe
Table 3. Parameters of hydrorgen bonds in structures Iс and
IVа
Angle, bond
Si1–O1
IVа
Vd
VIe
1.6150(5)a
Hydrogen
Ic
bond
1.6195(6)
1.6122(8)
Si1–C1
Si1–C2
Si1–C3
1.845(2)
1.855(2)
1.892(2)
1.6195(6)
3.6726(18)
4.110
1.843(2)
1.847(3)
1.887(2)
1.6122 (8)
3.8549(3)
1.8608(15)
1.8446(19)
1.8881(16)
1.6149(5)
D–H···A
D–H···A
D–H (Å)
H···A (Å)
2.13(2)
D···A (Å)
(deg)
O2–H2A'···Cl1 0.85(2)
2.9820(17)
175.8(5)
i
O2–H2B'···O3 0.850(13) 1.696(16) 2.541(2)
172(2)
167(2)
176(3)
O1–Si1
O3–H3A'···Cl1 0.85(3)
2.288(19) 3.122(2)
i
Si1···O2
Si1···Cl1
Si1O1Si1
3.6496(18)a
O3–H3B'···Cl1 0.844(14) 2.255(11) 3.0976(18)
ii
180.0
180.00 (3)
180.0
IVа
a
The values for structure VIe relate to the Si1–O2 bond and Si1····O11
distance.
O2–H2O···Cl1
0.850(4)
2.018(4)
2.8558(19) 168.9(4)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 12 2011

SCHEME OF HYDROLYSIS OF FIVE-COORDINATE CHLOROSILANES
heated in a distillation flask for 15 min until
2435
chlorotrimethylsilane no longer distilled. After a few
days the residue crystallized to give 8.2 g (95%) of
crude chloride Iа, mp 84–86°С (mp 64–66°С [4],
purified by sublimation). Crystallization of the crude
product from a 1:1 ether–hexane mixture gave two
types of crystals: on the flask bottom under a layer of
solvent and on the flask walls in contact with air.
According to X-ray diffraction data, the first crystals
belong to chloride Iа and the second, to dihydro-
chloride IVа.
b. To 24.7 g of N-methyl-N-SiMe3-acetamide we
added dropwise 23 g of ClCH2SiMe2Cl, and the
mixture was heated until complete removal of
chlorotrimethylsilane (15.5 g, 89%). The residue
crystallized to give 26.7 g (87%) of chloride Iа. The
physiochemical and spectral parameters of the product
were consistent with those reported in [4, 44]. Crude
chloride Iа (14.5 g) was dissolved in 80 ml of benzene,
and the solution was left to stand in an open vessel in a
hood at room temperature. The crystals that remained
after the solvent evaporated almost completely were
suspended in 20 ml of hexane and filtered off to obtain
14 g (93%) of dihydrochloride IVа, mp 99–103°С
(dioxane). IR spectrum (CHCl3), ν, cm–1: 3200–3100
br (CH, OH), 1600 s (C=O). 1Н NMR spectrum
(CDCl3), δН, ppm: 0.22 s (12H, SiMe2), 2.14 s (6H,
CH3C), 2.80–2.90 m (4Н, SiCH2), 3.09 s (6Н, CH3N).
13С NMR spectrum (CDCl3), δC, ppm: 4.52 (SiMe2),
17.35 [MeC(O)], 37.91 (NCH2), 43.07 (NMe2), 173.12
(С=О). 29Si NMR spectrum (CDCl3): δSi –3.1 ppm.
Found, %: С 38.05; Н 8.14; N 7.81. C12H30Cl2N2O3Si2.
Calculated, %: С 38.18; Н 8.01; N 7.42.
Fig. 5. General view of a molecule of disiloxane VIe in
crystal (H atoms are not shown).
(SiMe2), 23.50 [MeC(O)], 26.93 (NCH2), 41.02
(NMe2). 29Si NMR spectrum (CDCl3): δSi 3.2 ppm.
Found, %: С 47.33; Н 9.27; N 9.20. C12H28N2O3Si2.
Calculated, %: С 47.09; Н 9.63; N 9.42.
1,1,3,3-Tetramethyl-1,3-bis[(2-oxohexahydro-
azepin-1-yl)methyl]-1,3-disiloxane dihydrochloride
([L7CH2SiMe2]2O·2HCl) (IVb). Chloro(dimethyl)[(2-
oxohexahydroazepin-1-yl)methyl]silane (Ib), 1.7 g,
was dissolved in 20 ml of benzene, and the solution
was left to stand in an open vessel in a hood at room
temperature. The crystals that remained after the sol-
vent evaporated almost completely were suspended in
5 ml of heptanes and filtered off to obtain 1.6 g (89%)
of dihydrochloride IVb, mp 99–103°С (ether). IR
spectrum (CHCl3), ν, cm–1: 3200–3100 br (CH, OH),
1
Hydrolysis of N-(dimethylchlorosilylmethyl)-N-
methylacetamide Iа in the presence of a base.
1,1,3,3-Tetramethyl-1,3-bis(N-methylacetamido-
methyl)-1,3-disiloxane (Vа). To a solution of 13 g of
chloride Iа in 40 ml of CHCl3 we added dropwise with
stirring a solution of 6.1 g of NaHCO3 in 20 ml of
water, and the mixture was stirred for 3 h. After a day
the organic layer was separated, and the aqueous layer
was extracted with chloroform (3×10 ml). The com-
bined organic extracts were dried over calcinated
K2CO3, chloroform was removed by distillation, anв
the residue was fractionated to obtain 9 g (85%) of
disiloxane Vа, mp 197–201°С (7 mm), nD20 1.4725. IR
1640 s (C=O). Н NMR spectrum (CDCl3), δ, ppm:
0.42 s (12H, SiMe2), 2.89 s (4H, NCH2), 2.52 m (4H,
H3), 1.51–1.83 m (12H, H4–6), 4.54 m (4Н, Н7), 6.54
br.s (2H, HCl). 29Si NMR spectrum (CDCl3): δSi
–3.2 ppm. Found, %: С 47.08; Н 8.43; Si 12.22.
C18H38N2O3Si2. Calculated, %: С 47.25; Н 8.37; Si
12.22.
Synthesis of N-(chlorodimethylsilylmethyl)-2-azo-
canone (Ic) and dimethyl[(2-oxoazpcan-1-yl)methyl]-
silyloxonium chloride (IIIc). а. To a solution of 2 g
of N-SiMe3-enantolactam [37] in 8 ml of absolute
benzene we added dropwise with stirring 1.43 g of
ClCH2SiMe2Cl (the reaction mixture warmed up to
~50°С). After a day part of crystals that formed was
taken for X-ray diffraction analysis which showed that
they belong to chloride Ic. The remaining crystals
1
spectrum (CHCl3), ν, cm–1: 1630 s (C=O). Н NMR
spectrum (CDCl3), δ, ppm: 0.22 s (12H, SiMe2), 2.14 s
(6H, CH3C), 2.80–2.90 m (4Н, SiCH2), 3.09 s (6Н,
CH3N). 13С NMR spectrum (CDCl3), δC, ppm: –0.01
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 12 2011

2436
SHIPOV et al.
Table 4. Principal measurement and refinement parameters for structures I–VI
Parameter
Brutto formula
Molecular weight
Space group
Z
Ia
Ic
IIа
IIIc
IVа
Vd
VIe
C6H14ClNOSi C16H26ClNOSi C11H16ClNOSi C20H48Cl2N2O6Si2 C12H30Cl2N2O3Si2 C22H24N2O5Si2 C24H28N2O5Si2
179.72
I41
311.92
P2(1)/c
4
241.79
P21/c
4
539.68
С2/с
4
377.46
P21/n
2
452.61
P-1
1
480.66
P21/n
2
16
a, Å
b, A
20.985(6)
20.985(6)
9.9024(17)
21.877(4)
12.174(5)
11.914(4)
29.564(7)
6.5023(10)
13.771(2)
7.687(4)
8.309(3)
9.0743(16)
13.937(2)
6.6436(15)
c, A
8.773(2)
8.7971(15)
8.693(3)
16.692(4)
11.6576(19)
10.077(5)
10.1789(17)
α, deg
β, deg
γ, deg
90.00
90.00
90.00
90.00
115.333(4)
90.00
90.00
92.253(7)
90.00
90.00
117.841(4)
90.00
90.00
104.452(3)
90.00
106.87(3)
90.95(3)
108.92(3)
90.00
105.883(4)
90.00
V, Å3
3863.3(18)
1.236
4.63
1722.5(5)
1.203
2.88
1259.8(8)
1.275
3.74
2899.0(12)
1.237
3.41
1010.8(3)
1.240
4.49
578.3(5)
1.300
1.88
1238.2(4)
1.289
1.8
dcalc, g cm–3
μ, cm–1
F(000)
1536
672
512
1168
404
238
508
2θmax, deg
60
60
57
60
60
56
60
Reflections meas-
ured
22793
12677
12546
8463
11856
4376
12107
Unique reflec-
tions
5602
4630
181
4933
3424
199
3210
1770
139
4108
3191
241
2938
2206
157
2695
2241
142
3601
2231
152
Reflections with
I > 2σ(I)
Number of re-
fined parameters
R1
0.0576
0.1466
0.0709
0.1918
0.0642
0.1263
0.0622
0.1685
0.0596
0.1488
0.0696
0.2085
0.0470
0.1430
wR2
GОOF
1.009
0.995
0.991
0.998
1.062
1.090
0.980
Residual electron 0.960/–0.399 1.867/–0.293 0.672/–0.360
density, e A–3
1.613/–0.432
1.664/–0.326
1.385/–0.404 0.419/–0.145
(dmin/dmax
)
were filtered off to isolate 2 g (87%) of chloride Ic, mp
109–114°С. IR spectrum (CHCl3), ν, cm–1: 1600 s,
Recrystallization of part of the synthesized chloride
Iс from benzene without special protection from air
moisture gave, according to X-ray diffraction and
elemental analysis data, hydrate IIIc·H2O, mp 73–75°С.
IR spectrum (CHCl3), ν, cm–1: 3040 s, 2980 w (СН,
1
1510 m (NCO). Н NMR spectrum (CDCl3), δ, ppm:
0.55 s (6Н, SiMe2), 1.39–1.78 m (8Н, Н4–7), 2.46 m
(2Н, Н3), 2.76 s (2Н, NCH2), 3.50 m (2Н, Н8). Since
chloride Ic fairly rapidly hydrolyzed in CDCl3, we
could not obtain 13С and 29Si NMR spectra of a pure
sample.
1
ОН), 1580 s, 1500 m (NCO). Н NMR spectrum
(CDCl3), δ, ppm: 0.38 s (6Н, SiMe2), 1.35–1.76 m
(8Н, Н4–7), 2.48 m (2Н, Н3), 2.75 s (2Н, NCH2), 3.49
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 12 2011

SCHEME OF HYDROLYSIS OF FIVE-COORDINATE CHLOROSILANES
2437
m (2Н, Н8), 4.9 br.s (2Н, О+H2Cl). 13С NMR spectrum
(CDCl3), δC, ppm: 3.76 (SiMe2), 23.77 (C7), 25.50
(C4), 27.43 (C6), 28.28 (C5), 29.9 (C3), 39.50 (NCH2),
48.35 (C8), 177.56 (C=O). 29Si NMR spectrum
(CPMAS): δSi –47.1 ppm. Found, %: С 44.64; Н 9.00;
N 5.17. C10H24ClNO3Si. Calculated, %: С 44.51; Н
8.96; N 5.19.
30 min after chlorotrimethylsilane had stopped to
evolve and the reaction mixture cooled down to room
temperature, it was diluted with 30 ml of hexane.
Crystals formed and were filtered off to obtain 6.81 g
(43%) of disiloxane Vd (per N-SiMe3-phthalimide),
mp 135–137°С (hexane–benzene, 3:1). IR spectrum
(CHCl3), ν, cm–1: 1765 w, 1685 s (С=О), 1617 w (Ar).
1Н NMR spectrum (CDCl3), δ, ppm: 0.12 s (12H,
SiMe2), 3.11 s (4H, NCH2), 7.61–7.75 m (8Н, Ar). 13С
NMR spectrum (CDCl3), δC, ppm: 0.35 (SiMe2), 29.89
(NCH2), 132.41, 133.66, 122.95, 168.42 (CAr). 29Si
NMR spectrum (CDCl3): δSi 0.7 ppm. Found, %: С
58.43; Н 5.19; N 6.24. C22H24N2O5Si2. Calculated, %:
С 58.38; Н 5.34; N 6.19.
b. The reaction of 4 g of N-SiMe3-enantolactam and
2.9 g of ClCH2SiMe2Cl in hexane gave 4.2 g (90%) of
chloride Ic. The product was recrystallized from
benzene to obtain, according to the elemental analysis,
silyloxonium chloride IIIc, mp 87–94°С. Found, %: С
48.09; Н 8.86; N 5.62. C10H22ClNO2Si. Calculated, %:
С 47.70; Н 8.80; N 5.56.
b. To chloro(chloromethyl)dimethylsilane, 14.3 g,
heated to 50°C were added dropwise 15.35 g of N-
SiMe3-phthalimide [39] in 20 ml of CH2Cl2, and the
mixture was heated until the solvent (CH2Cl2) and the
chlorotrimethylsilane formed (~29 ml) had been
removed completely. After a day the residue was
diluted with 50 ml of chloroform and then a solution of
12.6 g of NaHCO3 in 30 ml of water was added in
small portions with stirring. The resulting mixture was
stirred for 2 h and left to stand for a day, after which
the organic layer was separated, and the aqueous layer
was extracted with chloroform (3×10 ml). The
combined organic extracts were dried over calcinated
K2СО3, chloroform was removed in a rotary
evaporator, the crystals that remained were washed
with 125 ml of water, filtered off, and dried in air to
obtain 8 g (50.5%) of disiloxane Vd (per N-SiMe3-
phthalimide), mp 138–140°С (hexane–benzene, 1:1).
IR spectrum (CHCl3), ν, cm–1: 1765 w, 1685 s (С=О),
1617 w (Ar). 1Н NMR spectrum (CDCl3), δ, ppm: 0.12
s (12H, SiMe2), 3.11 s (4H, NCH2), 7.61–7.75 m (8Н,
Ar).
1,1,3,3-Тетраmethyl-1,3-bis[(2-oxoazocan-1-yl)-
methyl]disiloxane (Vc). а. To a solution of 8 g of N-
SiMe3-enantolactam in 20 ml of benzene we added
drowise 5.7 g of ClCH2SiMe2Cl, and the reaction
mixture was stirred for 2 h. In doing so, we observed
formation of a small amount of crystals. After a day
the reaction mixture was diluted with 20 ml of CHCl3,
a solution of 7 g of NaHCO3 in 40 ml of water was
then added, and the resulting mixture was stirred for
6 h. The organic layer was separated, the solvent was
removed in a rotary evaporator, and the residue was
fractionated to obtain siloxane 4.8 g of disiloxane Vc,
mp 260–261°С (4 mm), nD20 1.5000. IR spectrum
1
(CHCl3), ν, cm–1: 1615 s (C=O). Н NMR spectrum
(CDCl3) δ, ppm: 0.07 s (12H, SiMe2), 2.59 s (4H,
NCH2), 3.40 m (4H, H8), 2.39 m (4H, H3), 1.34–1.68
m (16H, H4–7). 13С NMR spectrum (CDCl3), δС, ppm:
174.57 (C=O), 0.64 (SiMe2), 23.71 (C7), 25.97 (C4),
27.85 (C6), 28.53 (C5), 33.10 (C3), 38.19 (NCH2),
29
48.71 (C8). Si NMR spectrum (CDCl3): δSi 1.0 ppm.
Found, %: С 58.14; Н 9.87; N 6.71. C20H40N2O3Si2.
Calculated, %: С 58.20; Н 9.77; N 6.79.
Hydrolysis of N-methyl-N-[chloro(methyl)phenyl-
silylmethyl]acetamide (IIа). а. In the presence of a
base. To a solution of 8.94 g of chloride IIa in 35 ml
of CHCl3 we added with stirring a solution of 4.32 g of
NaHCO3 in 60 ml of water, and the reaction mixture
was stirred for 4 h. After a day the organic layer was
separated, the aqueous layer was extracted with CHCl3
(3×15 ml), the chloroform extracts were evaporated in
a rotary evaporator, and the residue was fractionated to
obtain 3.79 g (48%) of 1,3-dimethyl-1,3-diphenyl-1,3-
bis(N-methylacetamidomethyl)-1,3-disiloxane (VIа),
mp 258–260°С (1 mm), nD20 1.5448. IR spectrum
b. To a mixture of 3.9 g of ammonium carbonate,
0.8 g of water, and 40 ml of CH2Cl2 we added with
stirring a solution of 2 g of IIIс·H2O in 40 ml of
CH2Cl2. After 5 days excess ammonium carbonate was
filtered off, the organic layer was separated and dried
over calcinated K2CO3, the solvent was removed in a
rotary evaporator, and the resdue was filtered off to
obtain 1.55 g (94%) of disiloxane Vс as an oil, nD20
1.4990.
Tteramethyl-1,3-bis(phthalimidomethyl)disiloxane
(Vd). а. To chloro(chloromethyl)dimethylsilane, 16.2 g,
heated to 50°С we added dropwise a solution of 15.35 g
of N-SiMe3-phthalimide [39] in 15 ml of CH2Cl2. In
1
(CHCl3), ν, cm–1: 1620 s (C=O). Н NMR spectrum
(CDCl3), δ, ppm: 0.47 s (6H, SiMe), 1.89 s (6H,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 12 2011

2438
SHIPOV et al.
CH3C), 2.81 s (6Н, CH3N), 2.98 s (4Н, SiCH2), 7.30–
7.60 m (10H, C6H5). 13С NMR spectrum (CDCl3), δС,
ppm: –0.01 (SiMe2), 23.50 [MeC(O)], 26.93 (NCH2),
41.02 [N(СН3)2]. Si NMR spectrum (CDCl3): δSi 3.2
ppm. Found, %: С 61.62; Н 7.52; N 6.56. C22H32·
N2O3Si2. Calculated, %: С 61.64; Н 7.52; N 6.54.
spectrum (CHCl3), ν, cm–1: 1780 w, 1680 s (С=О),
1600 w (Ar). 1H NMR spectrum (CDCl3), δ, ppm: 0.87
s (3H, SiMe), 3.33 д (2H, NCH2, 2JHH 15.4 Hz), 2.57 s
(4H, H3, H4), 7.37–7.63 m (5H, Ph). 13С NMR
spectrum (CDCl3), δC, ppm: 0.76 (SiMe), 27.71 (C3,
C4), 30.31 (NCH2), 128.32 (Co), 133.85 (Cм), 131.09
29
29
(Сп), 133.31 (Cи), 177.52 (C=O). Si NMR spectrum
b. In chloroform. Chloride IIа, 1 g, was dissolved
in a conical flask in 10 ml of wet chloroform, and the
solution was left to stand in air. Chloroform
evaporated within 5 days. The IR spectrum of the
residue and its melting point (120–124°С) were the
same as those of the starting chloride IIа.
(CDCl3): δSi 15.2 ppm. Found, %: С 59.81; Н 5.84; N
5.81. C14H28N2O5Si2. Calculated, %: С 59.97; Н 5.87;
N 5.83.
ACKNOWLEDGMENTS
c. On heating in water. A mixture of 1 g of chloride
IIа and 10 ml of water were refluxed for 9 h in a
conical flask equipped with a reflux condenser. Water
was then evaporated to obtain 0.45 g of an oily liquid
whose Н NMR spectrum showed four groups of
broadened singlets assignable to methyl and methylene
protons of a mixture of oligosiloxanes HO–{Me[MeC·
The work was financially supported by the Russian
Foundation for Basic Research (project nos. 09-03-
00669, 10-03-00824, and 11-03-00655).
1
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