In:
Zeitschrift für Naturforschung B, Walter de Gruyter GmbH, Vol. 60, No. 10 ( 2005-10-1), p. 1054-1064
Abstract:
The syntheses of two cyclic diorganosilicon enamines =CH 2 ) [R = Ph (2a), Me (2b)] are described. These compounds react with 8-oxyquinoline leading to bis(oxinato)silicon complexes RPhSi(oxinate)2 [R = Ph (5a), Me (5b)] . Their X-ray structures reveal hexacoordination of the Si atom with the monodentate substituents in cis-positions and N atoms as well as O atoms in trans-positions. In crystalline dimethylbis(oxinato)silicon, Me 2 Si(oxinate) 2 (7), the silicon atom is only bicapped tetrahedrally coordinated, while for dichlorobis(oxinato)silicon, Cl 2 Si(oxinate) 2 (8), there is an octahedral coordination of the Si atom with chlorine atoms in trans-positions. This conclusion is based on the results of spectroscopic analysis (IR, 29 Si CP/MAS NMR) as well as quantum chemical calculations. The first example of a silicon-bis-oxinate with the N→Si dative bonds in a trans-arrangement has been detected in the hexacoordinate silicon tris-chelate (oxinate) 2 Si(PhN-CH 2 CH 2 -NPh) (11). Its configuration was proven by X-ray structure analysis. Thus, for hexacoordinate bis(oxinato)silicon compounds three new architectures were found which complement the previously established building pattern of the N,N’-cis-O,O’-trans-bis(oxinato)silicon complexes. The mer-tris(oxinato)siliconium cation (9 + ) (its configuration being proven by 1 H and 13 C NMR spectroscopy) features at least three coordination patterns with (O,O;N,N)-cis,cis-, -cis,trans- as well as -trans,cis-arrangements of two oxinate ligands.
Type of Medium:
Online Resource
ISSN:
1865-7117
,
0932-0776
DOI:
10.1515/znb-2005-1006
Language:
English
Publisher:
Walter de Gruyter GmbH
Publication Date:
2005
detail.hit.zdb_id:
2078109-X
detail.hit.zdb_id:
124635-5
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