752
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 4, April, 2006
Lazareva and Pestunovich
Found (%): C, 30.07; H, 4.78; N, 11.98. C6H12N2O6Si. Calcuꢀ
lated (%): C, 30.50; H, 5.12; N, 11.86. Compound 3 was recrysꢀ
tallized from CH2Cl2. The yield was 79%. Compound 3 decomꢀ
posed above 200 °C without melting. Found (%): C, 34.41;
H, 5.88; N, 6.51. C6H12ClNO3Si. Calculated (%): C, 34.36;
H, 5.77; N, 6.68.
solvent). For the nitrileꢀstabilized silatranyl cation
[(CD3CN)Si(OCH2CH2)3N]+TFPB– (TFPB is tetraꢀ
kis[3,5ꢀbis(trifluoromethyl)phenyl] borate), ∆δ is
0.74 ppm.10 The 29Si chemical shift for this cation
is δ –94.9.
We also synthesized compound 2 by metathesis reacꢀ
tions of 1ꢀchloroꢀ and 1ꢀbromosilatranes with metal salts.
References
1. M. T. AttarꢀBashi, C. Eaborn, J. Vencl, and D. R. M.
Walton, J. Organomet. Chem., 1976, 117, C87.
2. C. Chuit, R. J. P. Corriu, R. Perz, and C. Reys, Synthesis,
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and Y. Bull, Chem. Soc. Jpn, 1993, 66, 2638; R. Radinov and
E. S. Schnurman, Tetrahedron Lett., 1999, 40, 243; J. F.
Reichwein, S. T. Lacono, and B. L. Pagenkopf, Tetrahedron,
2002, 58, 3813.
M = Li, Ag; X = Cl, Br
The IR and NMR data for the products obtained were
identical with those for compound 2.
1ꢀHydrosilatrane (1) reacted with CuCl2 much more
slowly: the reaction was completed over several hours.
3. M. G. Voronkov and M. S. Sorokin, Zh. Obshch. Khim.,
1986, 56, 1098 [J. Gen. Chem. USSR, 1986, 56 (Engl.
Transl.)].
4. G. Cerveau, C. Chuit, E. Colomer, R. J. P. Corriu, and
C. Reys, Organometallics, 1990, 9, 2415.
5. I. S. Birgele, A. A. Kemme, E. L. Kupche, I. B. Mazheika,
and V. D. Shatts, Kremniiorganicheskie proizvodnye
aminospirtov [Organosilicon Derivatives of Amino Alcohols],
Ed. E. Ya. Lukevics, Zinatne, Riga, 1987, 230 pp. (in
Russian).
6. E. Lukevics, L. Ignatovich, L. Golomba, Ju. Popelis, and
S. Belyakov, Main Group Metal Chem., 2000, 23, 761.
7. L. Bellamy, Advances in Infrared Group Frequencies, Methuen
and Co. LTD, Bungay, Suffolk, 1968.
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M. G. Voronkov, Izv. Akad. Nauk Latv. SSR, Ser. Khim.
[Bull. Acad. Sci. Latv. SSR, Div. Chem. Sci.], 1973, 365 (in
Russian).
The physicochemical characteristics and spectroscopic
data for compound 3 (see Table 1) are identical with
those for 1ꢀchlorosilatrane.11
Redox reactions with compound 1 as a reducing agent
remain poorly investigated. The results we presented here
can be used to develop new methods for the synthesis of
silatranes and obtain further data on the structure of the
silatranyl cation.
9. A. R. Cherkasov, V. I. Galkin, and R. A. Cherkasov, Usp.
Khim., 1996, 65, 695 [Russ. Chem. Rev., 1996, 65 (Engl.
Transl.)].
Experimental
10. S. R. Bahr and P. Boudjouk, J. Am. Chem. Soc., 1993,
115, 4514.
11. M. G. Voronkov, V. P. Baryshok, L. P. Petukhov, V. I.
Rakhlin, R. G. Mirskov, and V. A. Pestunovich, J. Organomet.
Chem., 1988, 358, 39.
12. G. I. Zelchan and M. G. Voronkov, Khim. Geterotsikl.
Soedin., 1967, 371 [Chem. Heterocycl. Compd., 1967 (Engl.
Transl.)].
13. A. J. Gordon and R. A. Ford, The Chemist’s Companion.
A Handbook of Practical Data, Techniques and References,
John Wiley and Sons, New York, 1972.
NMR spectra were recorded on a Brukerꢀ400 spectrometer
in CD3CN (20% solutions) with Me4Si or cyclohexane as the
internal standard. IR spectra were recorded on a Specord IR75
spectrometer (in KBr pellets). 1ꢀHydroꢀ, 1ꢀchloroꢀ, and
1ꢀbromosilatranes were prepared as described earlier.11,12 Solꢀ
vents were purified according to known procedures.13 All synꢀ
theses were carried out under dry argon.
Reactions of 1ꢀhydroꢀ and 1ꢀhalosilatranes with metal salts
(general procedure). A solution of an appropriate salt (0.001 mol)
in MeCN (30 mL) was added dropwise to a solution of an
appropriate silatrane (0.001 mol) in thoroughly dried acetoniꢀ
trile (10 mL). After the reaction was completed (monitoring by
1H NMR spectroscopy), the solution was decanted and concenꢀ
trated in vacuo and the residue was dried in vacuo. Compound 2.
Received January 10, 2006;
in revised form March 27, 2006