Pentacoordinated chlorosilanes with C,O-chelate ligands derived from N-methyl-N'-organosulfonyl-prolinamides

Nikolin, A. A.; Arkhipov, D. E.; Shipov, A. G.; Kramarova, E. P.; Koval'chuk, N. A.; Korlyukov, A. A.; Negrebetsky, V. V.; Baukov, Yu. I.; Bassindale, Alan; Taylor, P. G.; Bowden, A. and Bylikin, S. Yu. (2012). Pentacoordinated chlorosilanes with C,O-chelate ligands derived from N-methyl-N'-organosulfonyl-prolinamides. Chemistry of Heterocyclic Compounds, 47(12) pp. 1565–1583.

DOI: https://doi.org/10.1007/s10593-012-0949-7

Abstract

The reaction of amides RSO2-Pro-NHMe with ClCH2SiMe2Cl in the presence of (Me3Si)2NH gave pentacoordinated chlorosilanes RSO2-Pro-N(Me)CH2SiMe2Cl with an organosulfonyl group (R = Me, Ph, 4-ClC6H4, 4-BrC6H4, 4-MeC6H4, and 4-O2NC6H4) attached to the proline nitrogen atom. An alternative method for the preparation of these compounds comprises the cyclosilylmethylation of proline methylamide by dimethylchloromethylchlorosilane to give the previously unreported heterocyclic 2-sila-5-piperazinone system in the first step. The bicyclic silacyclane synthesized is 2-sila5-piperazinone condensed with a proline residue. The action of sulfonyl chlorides RSO2Cl leads to cleavage of the sila ring Si-N bond to give the desired chlorosilanes. The hydrolysis of these products, depending on the reaction conditions, gives either silyloxonium chlorides [RSO2-ProN(Me)CH2SiMe2OH2]Cl or disiloxanes [RSO2-Pro-N(Me)CH2SiMe2]2O. X-ray diffraction structural analysis showed that the silicon atom in the chlorides and silyloxonium chlorides is pentacoordinated due to an intramolecular O→Si bond and has distorted trigonal-bipyrimidal configuration. Si-29 NMR spectroscopy showed that the disiloxanes and bicyclic sila-5-piperazinone have a tetracoordinated silicon atom.

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