Facile base-free addition of methanol to PtII-activated nitriles. X-ray structure of a platinum(II) complex bearing unsymmetrical N-bound urea

The nitrile complex [Pt(dpa)(NCNMe2)2](SO3CF3)2·2H2O (2·2H2O) was prepared by treatment of [PtI2(dpa)] with AgSO3CF3 in dimethylcyanamide. When the abstraction of the iodide ligand was performed in a RCN–MeOH mixture, the imino ester complexes [Pt(dpa){NHC(OMe)R}2](SO3CF3)2 (R = Me 3, NMe2 4) were formed and these species were isolated in 76% and 70% yields, respectively. Complexes 3 and 4 were also generated when [Pt(dpa)(NCMe)2](SO3CF3)2 (1) and 2·2H2O, correspondingly, were dissolved in MeOH. The formulation of complexes was supported by agreeable ESI+-MS, IR, 1H and 13C{1H} NMR spectroscopies; the structure of 4 was determined by the single-crystal X-ray diffraction.