Facile nucleophilic substitution of coordinated acetonitrile in trans-[PtCl4(NCMe)(PPh3)]

Despite the generally accepted inertness of platinum(IV) complexes towards nucleophilic substitution, the title compound promptly reacts with nucleophiles L (L = pyridine, quinoline, isoquinoline, benzothiazole, o-, m-, p-toluidine) affording the corresponding acetonitrile substitution products. To follow the reaction spectroscopically, a series of platinum(IV) standards were prepared by bridge splitting of trans- [Pt(μ-Cl)Cl(PPh3)]2, followed by oxidation by PhICl2. All the new platinum(II) and platinum(IV) complexes were fully characterized, and, in some cases, the structure was studied by single crystal X-ray diffraction. Even when protic o-, m- and p-toluidines were used, chemoselectivity towards substitution was observed, with addition products formed in less than 10% extent.