Transition metal–carbon bonds. Part XXV. Allylic palladium complexes containing cyanide or azide ligands

Abstract

Cyano-bridged π-allylic palladium complexes of the type [Pd(CN)(all)]₄(all = 2-methylallyl, 1,2,3-trimethylallyl, or 1,1,3,3-tetramethylallyl) are made by treating [PdCl(all)]₂ with sodium cyanide (1 mol per g-atom Pd). These cyano-complexes react with tertiary phosphines or tertiary arsines (L) to give mononuclear complexes, [Pd(CN)all)L], having asymmetrically bonded allylic ligands, with 2 mol of sodium cyanide per g atom Pd, [PdCl(2-methylallyl)]₂ gives [Pd(CN)₂(2-methylallyl)]^–. ¹H N.m.r. and i.r. data are given and discussed.