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Tertiary arsine-stabilised arsenium salts: Syntheses and comparisons with phosphine analogues

Citation

Kilah, NL and Weir, ML and Wild, SB, Tertiary arsine-stabilised arsenium salts: Syntheses and comparisons with phosphine analogues, Dalton Transactions, (18) pp. 2480-2486. ISSN 1477-9226 (2008) [Refereed Article]

Copyright Statement

Copyright 2008 The Royal Society of Chemistry

DOI: doi:10.1039/b800965a

Abstract

The first tertiary arsine-stabilised arsenium salts, [(L)AsMePh]OTf (L = Ph3As, Me2PhAs, [2-(MeOCH2)C6H4]Ph2As, [2-(MeOCH2)C6H4]Me2As), have been prepared by chloride abstraction from chloromethylphenylarsine with trimethylsilyl triflate in the presence of the arsine. The complexes have been characterised by crystallography and 1H NMR spectroscopy. The chiral cations in the complexes have structures based on the trigonal pyramid in which the arsine is coordinated orthogonally to the prochiral, six-electron MePhAs+ ion that forms the base of the pyramid. The NMR data for the complexes in dichloromethane-d2 are consistent with rapid exchange of the arsine on the arsenium ion, even at 183 K. The corresponding phosphine-stabilised complexes are considerably more stable than their arsine counterparts in dichloromethane-d2 with the free energy of activation ΔGc = ca. 60 kJ mol-1 being calculated for phosphine exchange in [(Me2PhP)AsMePh]OTf at 281 K; for [(Me2{2-(MeOCH2)C6H4}P)AsMePh]OTf in the same solvent, ΔGc = ca. 70 kJ mol-1 at 323 K.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic Chemistry
Research Field:Non-metal Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Kilah, NL (Dr Nathan Kilah)
ID Code:84269
Year Published:2008
Web of Science® Times Cited:18
Deposited By:Chemistry
Deposited On:2013-05-01
Last Modified:2013-05-30
Downloads:0

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