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.