O,O-Monochelate complexes of silicon and germanium halides: The derivatives of l-mandelic N,N-dimethylamide

Article abstract of DOI:10.1016/j.jorganchem.2008.10.026

Reactions of O-trimethylsilyl-l-mandelic N,N-dimethylamide (1) with tetrachlorosilane and tetrachlorogermane lead to O,O-monochelate complexes, [1-(dimethylcarbamoyl)-1-phenylmethoxy]trichlorosilane (2) and [1-(dimethylcarbamoyl)-1-phenylmethoxy]trichloro

Full text of DOI:10.1016/j.jorganchem.2008.10.026

Journal of Organometallic Chemistry 694 (2009) 244–248
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
O,O-Monochelate complexes of silicon and germanium halides: The derivatives
of L-mandelic N,N-dimethylamide
a
a
a
c
S.Yu. Bylikin a,b, , A.G. Shipov , E.P. Kramarova , Vad.V. Negrebetsky , A.A. Korlyukov ,
*
Yu.I. Baukov a, M.B. Hursthouse d, L. Male d, A.R. Bassindale b, P.G. Taylor b
a Russian State Medical University, Ostrovityanov St. 1, Moscow 117997, Russia
b The Open University, Milton Keynes, MK7 6AA, UK
c Nesmeyanov Institute of Organoelement Compounds, Vavilov St. 28, Moscow 119991, Russia
d University of Southampton, Highfield, Southampton, SO17 1BJ, UK
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 1 August 2008
Received in revised form 2 October 2008
Accepted 13 October 2008
Available online 22 October 2008
Reactions of O-trimethylsilyl-L-mandelic N,N-dimethylamide (1) with tetrachlorosilane and tetrachloro-
germane lead to O,O-monochelate complexes, [1-(dimethylcarbamoyl)-1-phenylmethoxy]trichlorosilane
(2) and [1-(dimethylcarbamoyl)-1-phenylmethoxy]trichlorogermane (3). Pentacoordination of silicon
and germanium in these complexes was confirmed by X-ray studies.
X-ray data show that the Si and Ge atoms in 2 and 3 have TBP environments where the ether oxygen
and two halogens are equatorial while the third halogen and the amide oxygen occupy axial positions.
The axial O–M and Cl–M (M = Si, Ge) distances are somewhat longer than those in similar compounds
of tetracoordinate silicon and germanium.
Keywords:
Hypervalent silicon and germanium
Synthesis
Monoanionic (O,O)-didentate ligands
X-ray diffraction study
Quantum-chemical calculations
Intramolecular coordination in compounds 1–3 and relative stabilities of different conformations of
their molecules were studied by quantum-chemical calculations.
Ó 2008 Elsevier B.V. All rights reserved.
1. Introduction
from chloromethyltrichlorogermane and racemic N,N-dimethyl-O-
trimethylsilylmandelic amide [10].
Compounds of hypercoordinate silicon and germanium have at-
tracted particular attention owing to their structural features, reac-
tivity and non-rigidity in solution. The complexes of these
elements with (C,O)-, (O,S)-, (N,O)-monoanionic and (O,O)-, (S,S)-,
(C,O)-, (O,S)-dianionic ligands have been studied in some detail
[1,2]. In particular, we have reported several synthetic approaches
to neutral penta- and hexacoordinate chlorosilanes and chloro-
germanes with amidomethyl, lactamomethyl and similar (C,O)-
chelate monoanionic ligands (see, for example, Refs. [3,4] and
references therein). The chelates with (O,O)-monoanionic ligands
have been less comprehensively studied [1b,2a]. These compounds
are represented by the derivatives of acetylacetone [4], tropolone
[5] and similar symmetrical ligands [6,7] and also by the deriva-
tives of 2-hydroxypyridine N-oxide and acylamides [8] (see also
[4c,9] and the citations therein). The synthesis, structure and
chemical transformations of another (O,O)-monochelate of penta-
coordinate germanium, [1-(dimethylcarbamoyl)-1-phenylmeth-
oxy]dichloro(chloromethyl)germane, were reported by us in a
preliminary communication [10]. The latter complex was prepared
We have found previously that unsubstituted and N-mono-
substituted amides of hydroxy acids could be used for the prep-
aration of pentacoordinate silicon [11] and germanium [12]
complexes with (C,O)-chelate amidomethyl ligands. In the pres-
ent paper we report the use of an N,N-disubstituted amide of
L-mandelic acid as the starting compound for the synthesis of
new (O,O)-monochelate complexes of pentacoordinate silicon
and germanium.
2. Results and discussion
We have found that reactions of SiCl4 and GeCl4 with N,N-
dimethyl-2-trimethylsiloxyamide (1) could be used as convenient
synthetic approaches to new complexes of pentacoordinate
silicon (2) and germanium (3) with monoanionic (O,O)-chelate
ligands. The reactions proceed in inert organic solvents at room
temperature and require about 24 h for completion. In the case
of L-mandelic amide the type of the complex is independent
of the ratio of reagents; reactions of one equivalent of GeCl4
with one or two equivalents of the amide led to the same
monochelate (3). In all experiments the yields of the complexes
2 and 3 with respect to MCl4 (M = Si, Ge) were from 81% to
86%.
* Corresponding author. Address: Russian State Medical University, Ostrovityanov
St. 1, Moscow 117997, Russia.
E-mail address: sbyl.rsmu@mtu-net.ru (S.Yu. Bylikin).
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.10.026

S.Yu. Bylikin et al. / Journal of Organometallic Chemistry 694 (2009) 244–248
245
respective distance is more than 3.0 Å, the angle between carbonyl
oxygen and the axial Ge–Cl bond is 160–180°) [17,22–24]. A possi-
ble reason for this is the participation of the carbonyl O atom in
intermolecular interactions which prevent the formation of the
Ge–O bond.
NMe2
O
NMe2
O
Ph
Ph
MCl4
Cl
Cl
–Me3SiCl
O
M
Cl
OSiMe3
The analysis of the intramolecular Oꢁ ꢁ ꢁSiMe3 distances in the
Cambridge Structural Database (981 ordered compounds) [8]
shows that these distances vary in the range of 2.51–3.48 Å and
the angles between the O atom and axial Si–Me bond from 150
to 180°. The number of compounds with the non-bonded intramo-
lecular Oꢁ ꢁ ꢁSiMe3 distance less than 3.0 Å is 281. Unfortunately,
there is a lack of information concerning the Oꢁ ꢁ ꢁSiCl3 distances.
We believe that the Si(Ge)ꢁ ꢁ ꢁO distance can be affected by crystal
packing at least in the cases of SiMe3 and GeCl3 complexes.
According to quantum-chemical studies of complexes with
the COSiMe2Cl coordination centre [25], the potential energy
curve (PEC) of the Si–O coordination bond is rather flat (the rel-
ative changes in energy do not exceed 5 kcal/mol in the range
of 2.0–2.5 Å), so molecules of 2a and 3a can exist both as coor-
dinated and non-coordinated isomers. In the present paper we
report the quantum-chemical study of possible isomers for
compounds 1a–3a. All calculations were performed for isolated
molecules using PBE0/6-311G(d) and MP2/6-311G(d) levels of
theory.
1a,b
2a (M = Si), 3a,b (M = Ge)
L-isomer (a), racemate (b)
The structures of all complexes were confirmed by IR spectros-
copy, 1H, 13C, 29Si NMR and elemental analysis. The chemical shifts
of 29Si in CDCl3 solutions of 1 and 2 (21.30 and ꢀ93.84 ppm, respec-
tively) confirm the tetracoordinated state of the Si atom in O-TMS
derivatives 1a,b and the pentacoordination of the central atom in
monochelates 2a,b [13]. The resonances of the NMe2 protons in
NMR 1H spectra of 1 and 2 appear as two singlets owing to the pres-
ence of chiral carbon centers in their molecules.
The IR spectrum of O-trimethylsilyl amide 1 contains two
strong bands at 1672 and 1652 cmꢀ1 (NCO fragment) and a weaker
band at 1620 cmꢀ1 (Ph group). The spectra of monochelates con-
tain two strong bands at 1676 and 1456 cmꢀ1 (2) or 1655 and
1484 cmꢀ1 (3) of the NCO vibrations.
3. Single crystal X-ray studies
The calculations confirm that non-coordinated isomers of com-
pounds 2a and 3a are less favorable than the respective chelates. In
contrast, the chelate of 1 would have a considerably higher poten-
tial energy than the acyclic isomer.
The details of the molecular structures of 1a–3a in the crystals
were investigated by single crystal X-ray studies. All molecules
crystallize in chiral space groups with the S configuration of C(2)
asymmetric atoms. Isostructural trichlorides 2a and 3a in the crys-
tals are characterized by pentacoordination of Si and Ge atoms. The
coordination polyhedron of the Si atom in 2a can be described as a
nearly ideal trigonal bipyramid, the deviation of this atom from the
plane formed by equatorial atoms O(2), Cl(2) and Cl(3) is 0.07 Å
while the O(1)Si(1)Cl(1) angle is 176.00(5)°. In molecule 3a the devi-
ation of the Ge atom from the plane formed by equatorial atoms is
greater (0.12 Å) than that for Si(1) atom in 2a. Five-membered che-
late rings in both compounds adopt envelope conformations with
the deviation of O(2) atom of 0.09 and 0.14 Å, respectively.
Data concerning pentacoordinate C,O- and O,O-chelated com-
pounds containing a Si(Ge)Cl3 moiety in the literature is limited
to a few complexes [14–18], in which the Ge–O distances vary in
the range of 2.08–2.51 Å. These data indicate that the Ge(1)–O(1)
coordination bond in 3a (1.9972(8) Å) is the strongest for this class
of compounds, probably due to the increased donor ability of the
NMe2 fragment as compared to the substituents at the C(1) atom
in other compounds. Despite this fact, the elongation of the axial
Ge(1)–Cl(1) bond in 3a (0.07 Å) is almost identical to that in previ-
ously reported complexes [14–19].
The length of the Si–O coordination bond in 2a (1.858(1) Å) is
close to Si–O distances in two complexes with C,O-ligands [20].
The axial Si(1)–Cl(1) bond is elongated in comparison with equato-
rial Si–Cl distances by 0.1 Å, which is noticeably shorter than in N-
(trichlorosilylmethyl)-hexahydroazepin-2-one (0.16 Å) [20].
In contrast to trichlorides 2a and 3a, the coordination Si–O bond
in trimethylsilyl ether 1a is absent, the interatomic separation of
Si(1) and O(2) atom is 3.33 Å, which is close to the sum of the
respective van der Waals radii [21]. The configuration of the
Si(1)C(2)C(1)O(1) moiety is non-planar; the value of the respective
torsion angle (67.8°) suggests that the Si(1)–O(2) coordination
bond is unfavorable due to significant conformational distortions.
The relaxed potential energy scan [PBE0/6-311G(d)] performed
using Si(1)ꢁ ꢁ ꢁO(1) and Ge(1)ꢁ ꢁ ꢁO(1) distances in 2a and 3a as coor-
dinates revealed two local minima corresponding to coordinated
and non-coordinated isomers. The calculated Si(Ge)ꢁ ꢁ ꢁO(1) dis-
tances in chelates are elongated by 0.15–0.3 Å as compared to
the experimental values found in structures 2a and 3a (Table 2).
The optimization of atomic coordinates using PBE0 and MP2 meth-
ods gives the similar values (2.166 and 2.187 Å) for the Ge(1)–O(1)
bond while the calculated values for Si(1)–O(1) bonds differ by
0.08 Å. In non-coordinated isomers of molecules 2a and 3a the
interatomic distances differ by 0.2 Å (Table 2). The C(1)–O(1) bonds
are shortened by 0.02 Å and the C(1)–N(1) bonds are shortened by
the same value in comparison with those in chelates. Also, the ab-
sence of Si(Ge)–O(1) coordination leads to significant shortening of
Si(Ge)–Cl and Si(Ge)–O(2) bonds (by 0.05 Å on average). The differ-
ences in potential energy between two isomers of molecule 2a are
3.9 and 1.5 kcal/mol, for PBE0/6-311G(d) and MP2/6-311G(d),
respectively. In the case of 3a these differences are somewhat lar-
ger (8.9 and 8.1 kcal/mol). Neither for 2a nor for 3a the transition
states corresponding to the formation of coordination bond were
located. This can be explained by the flexibility of five-membered
chelate rings in molecules 2a and 3a: the increase of potential en-
ergy due to the elongation of Si(Ge)–O coordination bonds is par-
tially compensated by the rotation of OCNMe2 group around the
C(1)–C(2) bond.
In the case of 1a the only one local minimum was found. The
Siꢁ ꢁ ꢁO distances calculated on PBE0 and MP2 level differ by
0.07 Å (Table 2). However, the calculated distances are consider-
ably (by as much as 0.4 Å) shorter than the experimental one. Tak-
ing into account the flatened PEC of Si(1)ꢁ ꢁ ꢁO(2) distance, the
possibility of significant coordination between these atoms can
be excluded. Thus the interatomic separation of Si and O atoms
is mainly a result of crystal packing forces. In particular, the O(2)
atom in the crystal forms three weak C–Hꢁ ꢁ ꢁO interactions with
the adjacent molecule (symmetry operation ꢀx, 0.5 + y, 0.5 ꢀ z;
the Hꢁ ꢁ ꢁO distances are 2.50–2.58 Å). The energies of these interac-
tions (several kcal/mol) can be sufficient for a significant increase
of the Siꢁ ꢁ ꢁO distance (Figs. 1–3).
4. Quantum-chemical calculations
According to the literature, there is a number of complexes with
Oꢁ ꢁ ꢁGeCl3 in which the Ge–O coordination is virtually absent (the

246
S.Yu. Bylikin et al. / Journal of Organometallic Chemistry 694 (2009) 244–248
Fig. 3. Molecular structure of 3a. Atoms are presented as thermal ellipsoids at 50%
probability.
The calculated elongation of the Si(Ge)–O(1) bonds in isolated
molecules 2a and 3a in comparison with the experimental values
can be explained similarly. The O(1) atom does not form intermo-
lecular contacts. On the other hand, the Cl(1) atoms in 2a and 3a
participate in 2–3 weak C–Hꢁ ꢁ ꢁCl interactions (the Hꢁ ꢁ ꢁCl distances
are 2.84–2.94 Å). Interactions of the same type are also observed
for equatorial Cl atoms. Their overall energy is comparable to the
energy needed for the shortening of the Si(Ge)ꢁ ꢁ ꢁO distances down
to their experimental values (2–3 kcal/mol, Fig. 4). The formation
of similar contacts in solution might cause the additional stabiliza-
tion of cyclic isomers and decrease the possibility of stereodynamic
processes involving the cleavage of the Si(Ge)–O(1) coordination
bond. Alternatively, in the case of molecule 1a intramolecular
interactions might hinder the Si(1)–O(2) bond formation and thus
prevent some dynamic processes (such as SiMe3 group exchange)
from taking place in solution.
Fig. 1. Molecular structure of 1a. Atoms are presented as thermal ellipsoids at 50%
probability.
Fig. 4. Potential energy curves calculated as potential energy surface scan of
molecules 1a–3a using Si(Ge)ꢁ ꢁ ꢁO(1) distance as coordinate at PBE0/6-311G(d) level
(range 1.8–4.35 Å, step size 0.05 Å).
Fig. 2. Molecular structure of 2a. Atoms are presented as thermal ellipsoids at 50%
probability.

S.Yu. Bylikin et al. / Journal of Organometallic Chemistry 694 (2009) 244–248
247
Table 3
5. Experimental
Crystallographic and experimental parameters of compounds 1a–3a.
IR spectra of compounds were recorded in KBr cells using a Spe-
cord IR-75 instrument. The 1H, 13C and 29Si NMR spectra in CDCl3
and CD3CN were recorded on a Jeol JNM-EX400 and a Varian
VXR-400 instruments (400.1, 100.6 and 79.5 MHz, respectively).
1H, 13C and 29Si chemical shifts were measured using tetramethyl-
silane as internal reference. All solvents were dried over molecular
sieves.
X-ray diffraction measurements of 1a–3a were carried out with
a Bruker Smart Apex II and Nonius Kappa CCD diffractometers. The
details of crystallographic data and experimental conditions are
presented in Table 1. Important structural parameters of structures
1a–3a are summarized in Table 2.
The structures were solved by direct method and refined by
full-matrix least-squares technique against F2 in the anisotropic–
isotropic approximation. Hydrogen atoms were located from dif-
ference electron density syntheses and refined in the rigid body
model. All calculations were performed using the SHELXTL PLUS 5.10
program package [26]. Atomic coordinates, bond lengths, bond an-
gles and thermal parameters of 1a–3a have been deposited at the
Cambridge Crystallographic Data Base (deposition numbers
694513, 694514 and 694628, respectively).
1a
2a
3a
Brutto formula
Formula weight
Diffractometer
C13H21NO2Si
251.40
Nonius Kappa Nonius Kappa
CCD
120
7.23190(10)
11.0720(3)
18.1646(5)
1454.47(6)
1.148
P212121, 4
27.47
544
C10H12Cl3NO2Si C10H12Cl3GeNO2
312.65
357.15
Bruker
SmartAPEX II
100
7.4003(3)
10.4878(5)
17.0299(8)
1321.74(10)
1.795
P212121, 4
33.14
712
CCD
120
Temperature (K)
a (Å)
b (Å)
7.38990(10)
10.4793(3)
17.0382(5)
1319.45(6)
1.574
P212121, 4
27.48
640
c (Å)
V (Å3)
dcalc. (g cmꢀ3
)
Space group, Z
2hmax (°)
F(000)
Scan type
Reflections collected
Independent reflections
U/
x
U/
x
x
18612
4961(0.0198)
17363
3314(0.0369)
11013
3014(0.0412)
[R(int)
]
Reflections with [I > 2
Parameters
r
(I)]
3142
160
1.53
2766
156
7.73
4760
156
29.12
Absorbtion coefficient
(cmꢀ1
R1 [I > 2
)
r(I)]
0.0457
0.1123
0.06(12)
0.0289
0.0616
0.08(6)
0.0166
0.0396
0.011(4)
wR2 (all reflections)
Absolute structure
parameter
Largest difference peak/hole 0.555/ꢀ0.985
0.265/ꢀ0.299
0.317/ꢀ0.748
(e Åꢀ3
)
Table 1
Selected experimental bond lengths, interatomic distances and bond angles in
molecules 1a–3a.
All quantum-chemical calculations were carried out using
PC-GAMESS program [27]. For geometry optimization and relaxed
potential surface scan of molecule 3a tight angular and radial grids
were utilized (NRAD = 99 and LMAX = 41) (Table 3).
1a
2a
3a
Si(Ge)–O(1)
1.655(1)
3.330(1)
1.867(2)
1.856(2)
1.864(2)
1.227(2)
1.351(2)
1.427(2)
1.535(2)
152.19
1.858(1)
1.665(1)
2.1693(7)
2.0740(8)
2.0720(8)
1.280(2)
1.309(3)
1.432(2)
1.517(3)
176.00(5)
114.2(2)
110.7(2)
ꢀ0.0708(5)
1.9972(8)
1.7872(8)
2.2253(3)
2.1495(3)
2.1465(3)
1.2760(1)
1.305(2)
1.424(1)
1.526(2)
173.95(3)
115.9(1)
107.70(9)
0.1241(3)
Si(Ge)ꢁ ꢁ ꢁO(2)
Si(Ge)–X(1) (X = C, Cl)
Si(Ge)–Y(2) (Y = C, Cl)
Si(Ge)–Y(3) (Y = C, Cl)
O(1)–C(1)
C(1)–N(1)
O(2)–C(2)
C(1)–C(2)
Cl(1)–Ge(1)–O(1)
O(1)–C(1)–C(2)
O(2)–C(2)–C(1)
DSi(Ge)
6. O-trimethylsilyl-
L-mandelic N,N-dimethylamide (1a)
Methyl- -mandelate (50 g, 0.30 mol) and Me2NH (50 g of
L
60 mass % aqueous solution, 0.62 mol) were mixed together and
kept in a sealed bottle for 3 days. The precipitate formed was fil-
tered, washed thoroughly with cold water (5 ꢂ 30 ml), and dried
120.1(1)
110.5(1)
0.5604(4)
in vacuo to afford 26 g (0.16 mol, 52%) of L-mandelic N,N-dimeth-
ylamide. The product was dissolved in hexamethyldisilazane
(52 g, 0.32 mol) and the mixture was refluxed for 3 h. The volatiles
were removed in vacuo and the residue was distilled to afford 35 g
(0.14 mol, 88%) of compound 1a, m.p. 42–43 °C (no solvent), b.p.
Table 2
87–89 °C (0.2 mm Hg). IR (CHCl3, m
, cmꢀ1): 1652 s, 1620 m. NMR
Selected calculated bond lengths, interatomic distances and bond angles in molecules
1a–3a.
1H (CDCl3, d, ppm): 0.15 s (9H, OSiMe3), 2.85 s, 2.89 s (6H,
NMe2), 5.50 s (1H, CH), 7.2–7.4 m (5H, Ph). NMR 13C (CDCl3, d,
ppm): ꢀ0.25 (OSiMe3), 36.29, 36.61 (NMe2), 76.42 (CH), 125.31,
127.48, 128.36, 138.99 (Ph), 171.50 (C@O). NMR 29Si (CDCl3, d,
Cyclic isomer
Acyclic isomer
PBE0/6-
311G(d)
MP2/6-
311G(d)
PBE0/6-
311G(d)
MP2/6-
311G(d)
ppm): 21.30. ½a 2D5
ꢃ
¼ þ42:8ꢄ (589 nm, MeCN, 0.2 M). Anal. Calc.
Molecule 1a
for C13H21NO2Si (mass %): C, 62.11; H, 8.42; N, 5.57; Si, 11.17.
Found (mass %): C, 62.45; H, 8.59; N, 5.78; Si, 10.92%. The crystals
for X-ray diffraction study were formed upon re-distillation of the
product.
Si(1)–O(1)
Si(1)ꢁ ꢁ ꢁO(2)
Si(1)–C
1.689
2.965
1.876
165.73
1.694
3.030
1.875
165.94
O(2)Si(1)C(1)
Molecule 2a
2.081
1.677
2.100
2.080
Si(1)ꢁ ꢁ ꢁO(1)
Si(1)–O(2)
Si(1)–Cl(1)
Si(1)–Cl(2)
Si(1)–Cl(3)
O(1)Si(1)C(1)
2.164
1.673
2.084
2.062
2.065
174.48
4.267
1.629
2.033
2.040
2.040
153.32
4.063
1.636
2.026
2.033
2.032
156.57
7. O-trimethylsilyl-DL-mandelic N,N-dimethylamide (1b)
2.077
5-Phenyl-1,3-dioxalan-4-one [28] (52 g, 0.31 mol) and Me2NH
(250 g of 30 mass % aqueous solution, 1.5 mol) were mixed together
and kept in a sealed bottle for 2 days. The precipitate formed was
filtered, washed thoroughly with cold water (5 ꢂ 30 ml), and dried
in vacuo to afford 33.6 g (0.19 mol, 60.5%) of DL-mandelic N,N-dim-
ethylamide. The crude product was dissolved in hexamethyldisilaz-
ane (100 g, 0.62 mol) and the mixture was refluxed for 3 h. The
volatiles were removed in vacuo and the residue was distilled to
174.39
Molecule 3a
2.166
1.795
2.177
Ge(1)ꢁ ꢁ ꢁO(1)
Ge(1)–O(2)
Ge(1)–Cl(1)
Ge(1)–Cl(2)
Ge(1)–Cl(3)
2.187
1.799
2.173
2.156
2.150
172.83
4.208
1.751
2.118
2.127
2.127
154.53
4.057
1.761
2.113
2.122
2.123
155.48
2.162
2.160
O(1)Ge(1)C(1) 172.28

248
S.Yu. Bylikin et al. / Journal of Organometallic Chemistry 694 (2009) 244–248
[2] (a) Yu.I. Baukov, S.N. Tandura, Z. Rappoport (Eds.), The Chemistry of Organic
Germanium, Tin and Lead Compounds, vol. 2, Wiley, London, 2002, pp. 963–
1239;
afford 42.1 g (0.17 mol, 90%) of compound 1b, b.p. 154–155 °C
(9 mm Hg), n2D0 1.4971. IR (CHCl3, , cmꢀ1): 1650 s, 1620 m. NMR
m
1H (CDCl3, d, ppm): 0.17 s (9H, OSiMe3), 2.81 s, 2.84 s (6H, NMe2),
5.52 s (1H, CH), 7.2–7.4 m (5H, Ph). NMR 13C (CDCl3, d, ppm):
ꢀ0.25 (OSiMe3), 36.25, 36.59 (NMe2), 75.40 (CH), 125.28, 127.48,
128.44, 138.99 (Ph), 173.20 (C@O).
(b) K.M. Mackay, S. Patai (Eds.), The Chemistry of Organic Germanium Tin and
Lead Compounds, Wiley, Chichester, 1995, pp. 97–194.
[3] (a) M.G. Voronkov, V.A. Pestunovich, Yu.I. Baukov, Metalloorg. Khim. 4 (1991)
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Antipin, A.G. Shipov, O.A. Zamyshlyaeva, E.P. Kramarova, Vad. V. Negrebetsky,
I.P. Yakovlev, Yu.I. Baukov, J. Organometal. Chem. 691 (2006) 3962;
(c) A.G. Shipov, E.P. Kramarova, S.A. Pogozhikh, Vad. V. Negrebetsky, L.S.
Smirnova, O.B. Artamkina, S. Yu. Bylikin, Yu.E. Ovchinnikov, Yu.I. Baukov, Russ.
Chem. Bull., Int. Ed. 56 (2007) 461.
8.
L
-[1-(Dimethylcarbamoyl)-1-phenylmethoxy]trichlorosilane
(2a)
[4] (a) E.P. Kramarova, G.I. Oleneva, A.G. Shipov, Yu.I. Baukov, Russ. J. Gen. Chem.
1 (1991) 1918. in Russian;
O-trimethylsilylamide 1a (3.77 g, 15 mmol) and SiCl4 (2.55 g,
15 mmol) were dissolved in hexane (20 ml) and stirred for 24 h.
The precipitate was filtered, washed with hexane (2 ꢂ 10 ml) and
dried in vacuo to afford 4.15 g (13 mmol, 88%) of compound 2a,
(b) E.P. Kramarova, G.I. Oleneva, A.G. Shipov, Yu.I. Baukov, A.O. Mozzhukhin,
M. Yu. Antipin, Yu.T. Struchkov, Organomet. Chem. USSR 4 (1991) 496;
(c) S.A. Pogozhikh, Yu.E. Ovchinnikov, S. Yu. Bylikin, Vad. V. Negrebetsky, A.G.
Shipov, Yu.I. Baukov, Russ. J. Gen. Chem. 70 (2000) 571. in Russian;
(d) S. Yu. Bylikin, E.P. Kramarova, S.A. Pogozhikh, A.G. Shipov, Vad. V.
Negrebetsky, Yu.E. Ovchinnikov, Yu.I. Baukov, Russ. Chem. Bull., Int. Ed. 2
(2003) 1720;
off-white crystals, m.p. 197–198 °C (MeCN). IR (KBr,
m
, cmꢀ1):
1676 s, 1456 m. NMR 1H (CDCl3, d, ppm): 2.75 s, 3.17 s (6H,
NMe2), 5.76 s (1H, CH), 7.4–7.6 m (5H, Ph). NMR 13C (CDCl3, d,
ppm): 38.92, 39.14 (NMe2), 75.88 (CH), 129.02, 130.74, 136.18,
138.75 (Ph), 174.47 (C@O). NMR 29Si (CDCl3, d, ppm): ꢀ93.84.
(e) E.A. Komissarov, A.A. Korlyukov, E.P. Kramarova, S.Yu. Bylikin, Vad.V.
Negrebetsky, Yu.I. Baukov, Acta Crystallogr., Sect. C 63 (2007) m144.
[5] (a) T. Ito, K. Toriumi, F.B. Ueno, K. Saito, Acta Crystallogr., Sect. B 36 (1980)
2998;
(b) P.S. Koroteev, M.P. Egorov, O.M. Nefedov, G.G. Aleksandrov, C.E. Nefedov,
I.L. Eremenko, Russ. Chem. Bull., Int. Ed. 49 (2000) 1800.
[6] A. Biller, C. Burschka, M. Penke, R. Tacke, Inorg. Chem. 41 (2002) 3901.
[7] C. Sterling, J. Inorg. Nucl. Chem. 29 (1967) 1211.
½
a 2D5
ꢃ
¼ þ35:8ꢄ (589 nm, MeCN, 0.2 M). Anal. Calc. for C10H12Cl3NO2-
Si (mass %): C, 38.42; H, 3.87; N, 4.48; Si, 8.98. Found (mass %): C,
38.81; H, 4.14; N, 4.44; Si, 8.07%. The crystals for X-ray diffraction
study were obtained from hot MeCN.
[8] Cambridge Structural database, Release, 2008.
[9] E.P. Kramarova, A.G. Shipov, Vad.V. Negrebetsky, S.Yu. Bylikin, E.A. Komissarov,
A.A. Korlyukov, Yu.I. Baukov, Russ. Chem. Bull., Int. Ed. 56 (2007) 1932.
[10] A.G. Shipov, E.P. Kramarova, T.P. Murasheva, Vad.V. Negrebetsky, S.Yu. Bylikin,
A.A. Korlyukov, Yu.I. Baukov, Russ. Chem. Bull., Int. Ed. 54 (2005) 2233.
[11] (a) A.B. Kurochka, A.S. Losev, E.A. Negrebetskaya, O.A. Zamyshlyaeva, Vad.V.
Negrebetsky, E.P. Kramarova, A.G. Shipov, Yu.I. Baukov, Russ. Chem. J. 48
(2004) 100 (in Russian);
9.
L-[1-(Dimethylcarbamoyl)-1-phenylmethoxy]trichloroger-
mane (3a)
O-trimethylsilylamide 1a (3.77 g, 15 mmol) and GeCl4 (3.22 g,
15 mmol) were dissolved in hexane (20 ml) and stirred for 24 h.
The precipitate was filtered, washed with hexane (2 ꢂ 10 ml) and
dried in vacuo to afford 4.50 g (13 mmol, 84%) of 3a, off-white crys-
(b) Yu.I. Baukov, A.G. Shipov, E.P. Kramarova, E.A. Mamaeva, O.A.
Zamyshlyaeva, N.A. Anisimova, Vad. V. Negrebetsky, Russ. J. Org. Chem. 32
(1996) 1216 (in Russian);
(c) A.G. Shipov, E.P. Kramarova, E.A. Mamaeva, O.A. Zamyshlyaeva, Vad. V.
Negrebetsky, Yu.E. Ovchinnikov, S.A. Pogozhikh, A.R. Bassindale, P.G. Taylor,
Yu.I. Baukov, J. Organometal. Chem. 620 (2001) 139;
(d) A.V. Kurochka, O.A. Afanasova, A.S. Losev, E.A. Mamaeva, S. Yu. Bylikin,
Vad.V. Negrebetsky, E.P. Kramarova, A.G. Shipov, Yu.I. Baukov, Met.-Based
Drug. 5 (1) (1998) 25;
(e) O.A. Zamyshlyaeva, A.G. Shipov, E.P. Kramarova, Vad. V. Negrebetsky, A.N.
Shumsky, S.N. Tandura, S. Yu. Bylikin, Yu.E. Ovchinnikov, S.A. Pogozhikh, Yu.I.
Baukov, Chem. Heterocycl. Comp. (1) (2002) 127.
tals, m.p. 238–239 °C (MeCN). IR (KBr, m
, cmꢀ1): 1655 s, 1484 m.
NMR 1H (CDCl3, d, ppm): 2.75 s, 3.14 s (6H, NMe2), 5.72 s (1H,
CH), 7.3–7.6 m (5H, Ph). NMR 13C (CDCl3, d, ppm): 38.40, 39.04
(NMe2), 75.87 (CH), 128.97, 130.58, 137.45, 139.20 (Ph), 174.34
(C@O).
½
a 2D5
ꢃ
¼ þ31:2 (589 nm, MeCN, 0.2 M). Anal. Calc. for
C10H12Cl3GeNO2 (mass %): C, 33.62; H, 3.39; Ge, 20.34; N, 3.92.
Found (mass %): C, 33.99; H, 3.53; N, 3.86; Ge, 19.80%. The crystals
for X-ray diffraction study were obtained from hot MeCN.
[12] S. Yu. Bylikin, E.P. Kramarova, A.G. Shipov, Vad. V. Negrebetsky, Yu.I. Baukov, J.
Gen. Chem. 47 (2001) 132 (in Russian).
[13] B. Wrakmeyer, Ann. Rep. NMR Spectr. 57 (2006) 1.
[14] A.A. Korlyukov, E.A. Komissarov, M. Yu. Antipin, N.V. Alekseev, K.V. Pavlov, O.V.
Krivolapova, V.G. Lahtin, E.A. Chernyshev, J. Mol. Struct. 875 (2008) 135.
[15] S.N. Gurkova, A.I. Gusev, N.V. Alexeev, T.K. Gar, N.A. Viktorov, Zh. Strukt. Khim.
(J. Struct. Chem.) 25 (1984) 170 (in Russian).
10. DL-[1-(Dimethylcarbamoyl)-1-phenylmethoxy]trichloroger-
mane (3b)
[16] .S.N. Gurkova, A.I. Gusev, N.V. Alexeev, T.K. Gar, N.A. Viktorov, Zh. Strukt. Khim.
(J. Struct. Chem.) 25 (1984) 174 (in Russian).
[17] S.A. Pogozhikh, Yu.E. Ovchinnikov, V.N. Khrustalev, M. Yu. Antipin, R.G.
Karpenko, S.P. Kolesnikov, Izv. Akad. Nauk, SSSR, Ser. Khim. (Russ. Chem. Bull.)
(1999) 116 (in Russian).
[18] S.N. Gurkova, A.I. Gusev, N.V. Alekseev, O.A. Dombrova, T.K. Gar, Metalloorg.
Khim. (Organomet. Chem. in USSR) 1 (1988) 1147 (in Russian).
[19] A.K. Nuridzhanyan, S.N. Gurkova, A.I. Gusev, V.F. Mironov, Izv. Akad. Nauk SSSR
Ser. Khim. (Russ. Chem. Bull.) (1993) 762 (in Russian).
[20] Yu.T. Struchkov, Yu.E. Ovchinnikov, A.G. Shipov, Yu.I. Baukov, Izv. Akad. Nauk
SSSR Ser. Khim. (Russ. Chem. Bull.) (1995) 1974 (in Russian).
[21] A. Bondi, J. Phys. Chem. 68 (1964) 441.
GeCl4 (5.3 g, 25 mmol) was added dropwise to the mixture of O-
trimethylsilylamide 1b (3.58 g, 20 mmol), Et3N (2.50 g, 25 mmol)
and benzene (15 ml). The mixture was stirred for 24 h, then diluted
with o-xylene (60 ml) and refluxed for a short time. Hot solution
was filtered from the precipitate and allowed to cool down to af-
ford 4.24 g (12 mmol, 47%) of racemate 3b, white crystals, m.p.
241–242 °C (MeCN).
This study was supported by Russian Foundation for Basic Re-
search (project 07-03-01067) and INTAS (project 03-51-4164).
[22] Shang-Guan, Guo-Qiang, S.-G. Zhang, Z.-S. Jin, J.-Z. Ni, Jiegou Huaxue, J. Struct.
Chem. 8 (1989) 177 (in Chinese).
[23] S.N. Gurkova, A.I. Gusev, N.V. Alexeev, T.K. Gar, N.A. Viktorov, Zh. Strukt. Khim.
(J. Struct. Chem.) 26 (1985) 14 (in Russian).
Appendix A. Supplementary material
[24] Shangguan Guoqiang, Zhang Shugong, Jin Zhongsheng, Liu Shuying, Ni.
Jiazuan, Wuli Huaxue Xuebao, Acta Phys.-Chim. Sin. 7 (1991) 223 (in Chinese).
[25] V.F. Sidorkin, E.F. Belogolova, V.A. Pestunovich, J. Mol. Struct. (Theochem.) 538
(2001) 59.
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.jorganchem.2008.10.026.
[26] G.M. Sheldrick, SHELXTL-97, Version 5.10, Bruker AXS Inc., Madison, WI-53719,
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