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

Lookup NU author(s): Dr Keith Izod, Emeritus Professor Bill Clegg, Dr Ross Harrington

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Abstract

The oxygen-bridged, silicon-substituted alkane {(Me3Si) 2CH(SiMe2)}2O (1) may be prepared by the reaction of {(Me3Si)2CH}Li with ClSiMe 2OSiMe2Cl in refluxing THF. Similarly, the alkane {(Me3Si)(Me2MeOSi)CH(SiMe2CH2)} 2 (2) is readily accessible from the reaction between {(Me 3Si)(Me2MeOSi)CH}Li and ClSiMe2CH 2CH2SiMe2Cl under the same conditions. Compound 1 reacts with two equivalents of MeK to give the polymeric complex {(Me 3Si)2C(SiMe2)}2OK 2(OEt2)∞ 5(OEt2) after recrystallisation. Treatment of 2 with two equivalents of either MeLi or MeK gives the corresponding complexes {(Me3Si)(Me2MeOSi) C(SiMe2CH2)}2LiLi(DME)3 7(DME) 3 and {(Me3Si)(Me2MeOSi)C(SiMe 2CH2)}2K2n (8), respectively, after recrystallisation. Treatment of the alkane (Me 3Si)2(Me2MeOSi)CH with one equivalent of MeK gives the polymeric complex {(Me3Si)2(Me 2MeOSi)C}K∞ (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(OEt 2) and 3 adopt polymeric structures in the solid state. © The Royal Society of Chemistry 2006.


Publication metadata

Author(s): Bowman LJ, Izod K, Clegg W, Harrington RW, Smith JD, Eaborn C

Publication type: Article

Publication status: Published

Journal: Dalton Transactions

Year: 2006

Issue: 3

Pages: 502-508

Date deposited: 09/07/2010

ISSN (print): 1477-9226

ISSN (electronic): 1477-9234

Publisher: Royal Society of Chemistry

URL: http://dx.doi.org/10.1039/b510692c

DOI: 10.1039/b510692c


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