Issue 14, 2016

Reduction of dichloro(diaza-phospha)stibanes – isolation of a donor-stabilized distibenium dication

Abstract

A reaction of antimonytrichloride SbCl3 with potassium bis(terphenylimino)phosphide K[(TerN)2P] smoothly afforded a novel class of mixed diazadipnictanes, namely dichloro(diaza-phospha)stibane [Ter2N2P(III)Sb(III)Cl2], which is considered to exist as open chain-like and cyclic isomers in an equilibrium. [Ter2N2PSbCl2] is a versatile starting material for reduction and halide abstraction experiments. Halide abstraction led to the formation of a cyclic diazastibaphosphenium cation [P(μ-NTer)2SbCl]+. Upon reduction of [Ter2N2PSbCl2], the transient existence of the novel mixed biradicaloid [P(μ-NTer)2Sb] was proven by a trapping experiment with an alkyne, while reduction in the absence of trapping agents afforded the eight-membered heterocycle [Sb2-{μ-(TerN)2P}2]. This constitutional isomer of a dimerized biradicaloid features a bonding situation that indicates the presence of a donor-stabilized [Sb2]2+ ion.

Graphical abstract: Reduction of dichloro(diaza-phospha)stibanes – isolation of a donor-stabilized distibenium dication

Supplementary files

Article information

Article type
Paper
Submitted
17 Jul 2015
Accepted
03 Aug 2015
First published
03 Aug 2015
This article is Open Access
Creative Commons BY license

Dalton Trans., 2016,45, 6044-6052

Author version available

Reduction of dichloro(diaza-phospha)stibanes – isolation of a donor-stabilized distibenium dication

A. Hinz, J. Rothe, A. Schulz and A. Villinger, Dalton Trans., 2016, 45, 6044 DOI: 10.1039/C5DT02711J

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