Two series of triphenylphosphine-stabilized diphenyl-arsenium, -stibenium, and -bismuthenium salts of the types [(Ph₃P)EPh₂]PF₆ (where E ) As, Sb, Bi) and [(Ph₃P)₂EPh₂]PF₆ (where E ) Sb, Bi) have been synthesized and their structures and bonding investigated by X-ray crystallography and density functional theory at the PBE/TZP level. The coordination geometries around the central group 15 elements are distorted trigonal pyramidal in the mono(triphenylphosphine) complexes and distorted trigonal bipyramidal in the bis(triphenylphosphine) complexes, where in each case the stereochemically active lone pair of the six-electron, angular diphenyl-arsenium, -stibenium, or -bismuthenium ion occupies an equatorial position in the trigonal plane containing the C-E-C bonds. For the complexes [(Ph₃P)EPh₂]- PF₆ (E = As, Sb, Bi), the theoretical results for the cations are consistent with the dative covalent formulation [Ph₃P→EPh₂]⁺, especially for E ) As and Sb, but for [(Ph₃P)₂EPh₂]PF₆ (E = Sb, Bi) the bonding between the phosphines and the stibenium or bisthmuthenium ion is best described as an induced dipole-ion interaction.

Item Type:	Refereed Article
Research Division:	Chemical Sciences
Research Group:	Inorganic chemistry
Research Field:	Main group metal chemistry
Objective Division:	Expanding Knowledge
Objective Group:	Expanding knowledge
Objective Field:	Expanding knowledge in the chemical sciences
UTAS Author:	Kilah, NL (Dr Nathan Kilah)
ID Code:	87070
Year Published:	2007
Web of Science® Times Cited:	44
Deposited By:	Chemistry
Deposited On:	2013-11-06
Last Modified:	2013-12-11
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