N-15 AND C-13 NMR-STUDIES ON CYCLOPALLADATED COMPLEXES - SYNTHETIC PALLADIUM CYANIDE CHEMISTRY LEADING TO ORGANIC NITRILES

15N NMR spectroscopy has been used to determine whether the 15NO group is coordinated in the cyclopalladated nitrosoamine complex [Pd(μ-OAc)(ONN-(CH3)C6H4)]2, PdCl{ONN(CH3)C6H4}{P(OMe)3} and K2[Pd(CN)3(ONN-(CH3)C6H4)], 11, as well as in several platinum(II) analogs. 13C NMR studies on 11, the cyclopalladated N,N-dimethylbenzylamine analog K2[Pd(CN)3(Me2NCH2C6-H4)], 12, and the dicyano cyclopalladated phosphite anion [Pd(CN)2{(PhO)2P)OC6H4}], 13, are useful in determining the coordination sphere of these molecules, and afford the novel coupling constants 2J(13CPd13C) cis and trans, between one cyanide and the palladated carbon. The complexes 11-13 are used as models to rationalize the reactions of 11 and 12 with (Bun4N)CN and diphos to form a 2-cyano-N-nitrosoaniline and a 2-cyano-N-dimethylbenzylamine. © 1990.