The open-chain triphosphanes RMe2SiCH2P(PR′2)2 (R = Me, Ph; R′ = SiMe3, Cy, Ph)

Averre, Charlotte E, Coles, Martyn P, Crossley, Ian R and Day, Iain J (2012) The open-chain triphosphanes RMe2SiCH2P(PR′2)2 (R = Me, Ph; R′ = SiMe3, Cy, Ph). Dalton Transactions, 41 (1). pp. 278-284. ISSN 1477-9226

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Abstract

The triphosphanes RMe2SiCH2P(PR2)2 (R = Me, Ph; R' = SiMe3, Cy) are synthesised in good yield via metathesis of organodichlorophosphanes and LiPR'2, while for R' = Ph a propensity to form (Ph2P)2 precludes isolation of the in-situ characterised triphosphanes. Where R=Me and R'=SiMe3 the triphosphane has also been characterised by single crystal X-ray diffraction and exhibits a single geometric conformer in the solid state, though solution-phase NMR spectra are indicative of facile conformational exchange across a wide temperature range. All of the described triphosphanes exhibit comparable behaviour, with their respective 31P{1H} NMR spectra manifesting anomalous 'second-order' characteristics, which are considered using full spin-Hamiltonian simulation. Preliminary studies of coordination chemistry and ancillary reactivity of the triphosphanes are described.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Subjects: Q Science
Depositing User: Martyn Coles
Date Deposited: 06 Feb 2012 19:53
Last Modified: 03 Oct 2012 11:04
URI: http://sro.sussex.ac.uk/id/eprint/22827
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