Nonlinear d(10)-ML(2) Transition-Metal Complexes

We have investigated the molecular geometries of a series of dicoordinated d(10)-transition-metal complexes ML(2) (M=Co(−), Rh(−), Ir(−), Ni, Pd, Pt, Cu(+), Ag(+), Au(+); L=NH(3), PH(3), CO) using relativistic density functional theory (DFT) at ZORA-BLYP/TZ2P. Not all complexes have the expected linear ligand–metal–ligand (L–M–L) angle: this angle varies from 180° to 128.6° as a function of the metal as well as the ligands. Our main objective is to present a detailed explanation why ML(2) complexes can become bent. To this end, we have analyzed the bonding mechanism in ML(2) as a function of the L–M–L angle using quantitative Kohn–Sham molecular orbital (MO) theory in combination with an energy decomposition analysis (EDA) scheme. The origin of bent L–M–L structures is π backdonation. In situations of strong π backdonation, smaller angles increase the overlap of the ligand’s acceptor orbital with a higher-energy donor orbital on the metal-ligand fragment, and therefore favor π backdonation, resulting in additional stabilization. The angle of the complexes thus depends on the balance between this additional stabilization and increased steric repulsion that occurs as the complexes are bent.