Synthesis of Homo‐ and Hetero‐Bimetallic Arsenic Complexes by Means of Regioselective Monoinsertion of Alkynylarsane into the Pd–C Bond of a Palladacycle

Cyclopalladated and cycloplatinated complexes, which incorporated the N , N ‐dimethylbenzylamine and N , N ‐dimethylnaphthylamine motifs, were successfully employed to promote a series of intermolecular monoinsertion reactions of diphenyl‐1‐propynylarsane, Ph 2 AsC≡CMe, into the Pd–C bond of the chiral α‐methyl N , N ‐dimethylbenzylamine palladacycles. The precursor complexes were prepared by means of the coordination of the Ph 2 AsC≡CMe moiety onto the metal center trans to the benzylamine– or naphthylamine–N donor atom of the cyclometallated complexes. Subsequently a series of monoinsertion reactions were carried out between these precursor complexes and the enantiomerically pure N , N ‐dimethyl benzylamine palladacycles. These insertion reactions showed high regioselectivity under mild conditions and a variety of homo‐ and heterobimetallic arsenic functionalized complexes were formed. The coordination chemistry and the absolute stereochemistry of the monoinsertion products were determined by X‐ray crystallography.