Reaction of trithiazyl trichloride, (NSCl)₃, with triphenylphosphine or triphenylphosphine metal complexes. X-Ray crystal structure of aminotriphenylphosphonium chloride–dichloromethane (1/1), [Ph₃PNH₂]Cl·CH₂Cl₂

Abstract

The reaction between (NSCl)3 and [RuCl2(PPh3)3] gives [RuCl3(NS)(PPh3)2] together with [Ph3PNH2]Cl·CH2Cl2(2)(characterised by X-ray crystallography, 31P n.m.r. and i.r. spectroscopy) and Ph3PNH (4). Reaction between (NSCl)3 and PPh3 also gives (2) and (4); a mechanism for this reaction is proposed. Reactions of (NSCl)3 with [RhCl(PPh3)3], trans-[Rh(CO)Cl(PPh3)2], or [Rh(NO)(PPh3)3] were investigated by 31P n.m.r. and contrary to several previous reports do not give thionitrosyl complexes but rather result in the formation of (2) and (4) or in the oxidation of the material to [Rh(CO)Cl3(PPh3)2]. The existence of any rhodium phosphine thionitrosyls is thus cast into doubt.