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

Abstract

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 AsCϵCMe, 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 AsCϵCMe moiety onto the metal center trans to the benzylamine-or naphthylamine-N

Nitrogen, phosphorus, arsenic, antimony and bismuth

“…110 The reaction of AsPh 2 (CRCMe) with cyclometallated palladium complexes initially forms the arsane complex 64. 111 Addition of more palladium precursor results in insertion by the pendant alkyne into the metal-carbon bond to afford 65.…”

Reactivity of Cycloplatinated Amine Complexes: Intramolecular C–C Bond Formation, C–H Activation, and PPh2 Migration in Coordinated Alkynylphosphines

“…From the literature reviews, it is also clear that these chiral auxiliaries are stable and that they are not directly involved in any chemical transformations and thus retain their structural and stereochemical integrity. In our recent effort to search for new chiral cyclometalated complexes as catalysts for asymmetric hydrophosphination reactions, however, we observed that the aromatic carbon–palladium bonds in ortho -palladated benzylamine complexes are indeed chemically reactive, as they undergo insertion reactions in the presence of coordinated alkynylphosphines. , On the other hand, the carbon–platinum bonds in the analogous ortho -platinated complexes are completely unreactive toward similar insertion reactions . Upon closer examination of the chemical behavior of these ortho -platinated benzylamine complexes, interestingly, we discovered that the organometallic chelates themselves can be activated by the presence of external platinum ions toward the aforementioned carbon–carbon bond formation.…”