Nucleophilic substitution reactions of the tricyclic triphosphorus cage P3(CBut)2: a novel route to polyphosphorus phosphenium complexes

Charlotte E. Willans; Cheryl Fish; Michael Green; Richard J. Kilby; Jason M. Lynam; Christopher A. Russell; Adrian C. Whitwood

doi:10.1039/B800864G

Nucleophilic substitution reactions of the tricyclic triphosphorus cage P₃(CBu^t)₂: a novel route to polyphosphorus phosphenium complexes†

Charlotte E. Willans,^a Cheryl Fish,^b Michael Green,*^b Richard J. Kilby,^b Jason M. Lynam,*^a Christopher A. Russell*^b and Adrian C. Whitwood^a

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* Corresponding authors

^a Department of Chemistry, University of York, Heslington, York, UK
E-mail: jml12@york.ac.uk
Fax: +44 (0)1904 432516
Tel: +44 (0)1904 4332534

^b School of Chemistry, University of Bristol, Cantock's Close, Bristol, UK
E-mail: Chris.Russell@bris.ac.uk
Fax: +44 (0)117 929 0509
Tel: +44 (0)117 928 7599

Abstract

Substitution of Cl⁻ in the tricyclic triphosphorus cage Cl(P¹)-P₃(CBu^t)₂ by a range of both anionic and neutral nucleophiles has been investigated. With anionic nucleophiles, reaction with fluoride and hydride anion was shown to afford F(P¹)-P₃(CBu^t) and H(P¹)-P₃(CBu^t)₂ respectively. Subsequent deprotonation of the latter results in the formation of the aromatic anion [1,2,4-P₃(CBu^t)₂]⁻. With neutral nucleophiles, addition of either PMe₃ or PEt₃ to Cl(P¹)-P₃(CBu^t)₂ in the presence of TlOTf results in the formation of the phosphine–phosphenium complexes [(R₃P(P¹)-P₃(CBu^t)₂][OTf] (R = Me or Et): the structure of the methyl-substituted compound was determined by a single crystal X-ray diffraction study. The phosphine ligand in these complexes is extremely labile and addition of I₂ to [(Me₃P(P¹)-P₃(CBu^t)₂]⁺ results in the formation of I(P¹)-P₃(CBu^t)₂.

This article is part of the themed collection: Main group chemistry: from molecules to materials

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Article information

DOI: https://doi.org/10.1039/B800864G
Article type: Paper
Submitted: 17 Jan 2008
Accepted: 27 Feb 2008
First published: 03 Apr 2008

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Dalton Trans., 2008, 3422-3428

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Nucleophilic substitution reactions of the tricyclic triphosphorus cage P₃(CBu^t)₂: a novel route to polyphosphorus phosphenium complexes

C. E. Willans, C. Fish, M. Green, R. J. Kilby, J. M. Lynam, C. A. Russell and A. C. Whitwood, Dalton Trans., 2008, 3422 DOI: 10.1039/B800864G

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