Synthesis and structural characterisation of various organosilane-organogermane and organosilane-organostannane statistical copolymers by the Wurtz reductive coupling polymerisation: Sn-119 NMR and EXAFS characterisation of the stannane copolymers

Mustafa, Alkay and Achilleos, Mariliz and Ruiz-Iban, J. and Davies, J. and Benfield, Robert E. and Jones, Richard G. and Grandjean, Didier and Holder, Simon J. (2006) Synthesis and structural characterisation of various organosilane-organogermane and organosilane-organostannane statistical copolymers by the Wurtz reductive coupling polymerisation: Sn-119 NMR and EXAFS characterisation of the stannane copolymers. Reactive & Functional Polymers, 66 (1). pp. 123-135. ISSN 1381-5148. (The full text of this publication is not available from this repository)

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http://dx.doi.org/10.1016/j.reactfunctpolym.2005.0...

Abstract

A number of polysilane-based copolymers with organogermanes and organostannanes have been prepared by the Wurtz-type reductive coupling of the corresponding dichlorodiorgano group 14 precursors. The copolymers synthesised were poly(di-n-butylgermane-c-o-methylphenylsilane), poly(di-n-butylgermane-co-n-hexylmethylsilane), poly(di-nbutylstannane-co-methylphenylsilane) and poly(methylphenylsilane-co-diphenylgermane). Poly(di-n-butylsilane) and poly(di-n-butylgermane) were also synthesised by the room temperature polymerisation of the dichloro-precursors in THF at room temperature and obtained in the highest reported yields to date from a Wurtz-type polymerisation. The polymers and copolymers were characterised by H-1, C-13, Si-29 and Sn-119 NMR spectroscopy and UV-vis spectroscopy. The Si-29 and Sn-119 NMR spectroscopic data provided unambiguous evidence for the incorporation of germane and stannane units into the predominantly polysilane backbones. The Sn-119 analysis is the first reported for such copolymers. UV-vis spectroscopy demonstrated that increasing the molar ratios of stannane:silane in the final copolymer led to a red-shift in the observed broad absorption peak. One of the organosilane-organostannane copolymers (PMPS-co-BuSn 2) was analysed by extended X-ray absorption fine-structure spectroscope (EXAFS) and X-ray absorption near-edge spectroscopy (XANES). Bond lengths were obtained for Sn-Sn (2.82 angstrom), Sn-Si (2.58 angstrom) and Sn-C (2.15 angstrom) and they correspond to those expected for Sri based compounds.

Item Type: Article
Additional information: 46 ELSEVIER SCIENCE BV
Subjects: Q Science > QD Chemistry
Divisions: Faculties > Science Technology and Medical Studies > School of Physical Sciences > Functional Materials Group
Depositing User: Simon Holder
Date Deposited: 29 Aug 2008 15:16
Last Modified: 09 May 2014 13:59
Resource URI: http://kar.kent.ac.uk/id/eprint/2561 (The current URI for this page, for reference purposes)
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