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Alkali metal complexes of sterically hindered mono- and di-carbanions containing Si-O bonds.

Authors :
Bowman LJ
Izod K
Clegg W
Harrington RW
Smith JD
Eaborn C
Source :
Dalton transactions (Cambridge, England : 2003) [Dalton Trans] 2006 Jan 21 (3), pp. 502-8. Date of Electronic Publication: 2005 Oct 26.
Publication Year :
2006

Abstract

The oxygen-bridged, silicon-substituted alkane {(Me3Si)2CH(SiMe2)}2O (1) may be prepared by the reaction of {(Me3Si)2CH}Li with ClSiMe2OSiMe2Cl in refluxing THF. Similarly, the alkane {(Me3Si)(Me2MeOSi)CH(SiMe2CH2)}2 (2) is readily accessible from the reaction between {(Me3Si)(Me2MeOSi)CH}Li and ClSiMe2CH2CH2SiMe2Cl under the same conditions. Compound 1 reacts with two equivalents of MeK to give the polymeric complex [[{(Me3Si)2C(SiMe2)}2O]K2(OEt2)]infinity [5(OEt2)] after recrystallisation. Treatment of 2 with two equivalents of either MeLi or MeK gives the corresponding complexes [{(Me3Si)(Me2MeOSi)C(SiMe2CH2)}2Li][Li(DME)3] [7(DME)3] and [{(Me3Si)(Me2MeOSi)C(SiMe2CH2)}2K2]n (8), respectively, after recrystallisation. Treatment of the alkane (Me3Si)2(Me2MeOSi)CH with one equivalent of MeK gives the polymeric complex [{(Me3Si)2(Me2MeOSi)C}K]infinity (3). These compounds have been identified by 1H and 13C{1H} NMR spectroscopy and elemental analyses and compounds 5(OEt2), 7(DME)3 and 3 have been further characterised by X-ray crystallography. Compound 7(DME)3 crystallises as a solvent-separated ion pair, whereas 5(OEt2) and 3 adopt polymeric structures in the solid state.

Details

Language :
English
ISSN :
1477-9226
Issue :
3
Database :
MEDLINE
Journal :
Dalton transactions (Cambridge, England : 2003)
Publication Type :
Academic Journal
Accession number :
16395450
Full Text :
https://doi.org/10.1039/b510692c