Oxidative addition of arsenic halides to platinum(0)

Reaction of AsCl3 with Pt(0) complexes [Pt(PCy3)2], [Pt(PCy3)(IMes)] and [Pt(IMes)2] (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) resulted in oxidative addition of As–Cl bonds at the Pt centres to form complexes of the form trans-[PtCl(AsCl2)L2]. Two of these compounds were characterised by X-ray diffraction, making them the first structurally characterised examples of AsX2 ligands (X = halogen). AsBr3 also underwent oxidative addition to [Pt(PCy3)2], forming trans-[PtBr(AsBr2)(PCy3)2] in situ, as judged by 31P NMR spectroscopy. This reaction was unselective, yielding several products, of which a Pt3As2 cluster could be identified by single-crystal X-ray diffraction.