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O,O-monochelate complexes of silicon and germanium halides: the derivatives of L-mandelic N,N-dimethylamide

Bylikin, S. Yu; Shipov, A. G.; Negrebetsky, Vlad V.; Korlyukov, A. A.; Baukov, Yu I.; Hursthouse, M. B.; Male, L.; Bassindale, A. R. and Taylor, P. G. (2009). O,O-monochelate complexes of silicon and germanium halides: the derivatives of L-mandelic N,N-dimethylamide. Journal of Organometallic Chemistry, 694(2) pp. 244–248.

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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]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.
Intramolecular coordination in compounds 1–3 and relative stabilities of different conformations of their molecules were studied by quantum-chemical calculations.

Item Type: Journal Article
Copyright Holders: 2008 Elsevier B.V.
ISSN: 0022-328X
Keywords: hypervalent silicon and germanium; synthesis; monoanionic (O,O)-didentate ligands; X-ray diffraction study; quantum-chemical calculations
Academic Unit/Department: Other Departments > Vice-Chancellor's Office
Other Departments
Science > Life, Health and Chemical Sciences
Interdisciplinary Research Centre: Biomedical Research Network (BRN)
Centre for Earth, Planetary, Space and Astronomical Research (CEPSAR)
Item ID: 17916
Depositing User: Colin Smith
Date Deposited: 20 Aug 2009 09:23
Last Modified: 15 Jan 2016 11:42
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