Nonlinear d(10)-ML2 Transition-Metal Complexes.

ABSTRACT: We have investigated the molecular geometries of a series of dicoordinated d(10)-transition-metal complexes ML2 (M=Co(-), Rh(-), Ir(-), Ni, Pd, Pt, Cu(+), Ag(+), Au(+); L=NH3, PH3, 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 ML2 complexes can become bent. To this end, we have analyzed the bonding mechanism in ML2 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

SUBMITTER: Wolters LP 

PROVIDER: S-EPMC3703815 | biostudies-literature | 2013 Jun

REPOSITORIES: biostudies-literature