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An Acyclic Arsenium Cation Stabilised by a Single P‐As π‐Interaction and a Cyclic Diphosphinophosphonium Salt

Lookup NU author(s): Dr Keith Izod, Peter Evans, Dr Paul Waddell



This is the authors' accepted manuscript of an article that has been published in its final definitive form by Wiley, 2019.

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Stable acyclic arsenium cations R2As+, isoelectronic analogues of germylenes, are rare in comparison to the corresponding phosphenium cations. The first example of a diphosphaarsenium salt [{(Dipp)2P}2As][Al{OC(CF3)3}4].1½PhMe (2) is described. This salt exhibits remarkable stability due to delocalisation of a lone pair from a planar phosphorus centre into the vacant p-orbital at arsenic; the bonding in 2 has been probed using DFT calculations. An attempt to synthesise an analogous diphosphaphosphenium salt unexpectedly generated the cyclic phosphonium salt [cyclo-{(Mes)P}2P(Mes)2][BArF4].CyMe (5.CyMe), via cyclisation of a putative phosphine-substituted diphosphene cation intermediate.

Publication metadata

Author(s): Izod k, Evans P, Waddell PG

Publication type: Article

Publication status: Published

Journal: Angewandte Chemie International Edition

Year: 2019

Volume: 58

Issue: 32

Pages: 11007-11012

Print publication date: 05/08/2019

Online publication date: 03/06/2019

Acceptance date: 03/06/2019

Date deposited: 11/06/2019

ISSN (print): 1433-7851

ISSN (electronic): 1521-3773

Publisher: Wiley


DOI: 10.1002/anie.201905922


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