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.