Carbodicarbene: <i>geminal</i>‐Bimetallic Coordination in Selective Manner

Abstract

Abstract The reaction of Pd(OAc) 2 with free carbodicarbene (CDC) generates a Pd acetate trinuclear complex 1 via intramolecular C(sp 3 )−H bond activation at one of the CDC methyl side arms. The solid structure of 1 reveals the capability of CDC to facilitate a double dative bond with two palladium centers in geminal fashion. This is attributed to the chelating mode of CDC, which can frustrate π‐conjugation within the CDC framework. Such effect maybe also amplified by ligand‐ligand interaction. The formation of other gem ‐bimetallic Pd−Pd, Pd−Au, and Ni−Au provides further structural evidence for this proof‐of‐concept in selective installation. Structural analysis is supported by computational calculations based on state‐of‐the‐art energy decomposition analysis (EDA) in conjunction with natural orbitals for chemical valence (NOCV) method.