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15N and13C NRM studies on cyclopalladated complexes Synthetic palladium cyanide chemistry leading to organic nitriles

Journal of Organometallic Chemistry
Publication Date
DOI: 10.1016/0022-328x(90)87015-6


Abstract 15N NMR spectroscopy has been used to determine whether the 15NO group is coordinated in the cyclopalladated nitrosoamine complex [Pd(μ-OAc)(ONN-(CH 3)C 6H 4)] 2, PdCl{ONN(CH 3)C 6H 4}{P(OMe) 3} and K 2[Pd(CN) 3(ONN-(CH 3)C 6H 4)], 11, as well as in several platinum(II) analogs. 13C NMR studies on 11, the cyclopalladated N,N-dimethylbenzylamine analog K 2[Pd(CN) 3(Me 2NCH 2C 6-H 4)], 12, and the dicyano cyclopalladated phosphite anion [Pd(CN) 2{(PhO) 2P)OC 6H 4}], 13, are useful in determining the coordination sphere of these molecules, and afford the novel coupling constants 2 J( 13CPd 13C) 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 (Bu n 4N)CN and diphos to form a 2-cyano- N-nitrosoaniline and a 2-cyano- N-dimethylbenzylamine.

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