title: 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 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.
authors.affiliation: Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, VU University De Boelelaan 1083, 1081 HV Amsterdam (The Netherlands).
authors.forename: Lando P
authors.initials: LP
authors.lastname: Wolters
authors.affiliation: Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, VU University De Boelelaan 1083, 1081 HV Amsterdam (The Netherlands) ; Institute for Molecules and Materials, Radboud University Nijmegen Heyendaalseweg 135, 6525 AJ Nijmegen (The Netherlands).
authors.forename: F Matthias
authors.initials: FM
authors.lastname: Bickelhaupt
keywords: bond theory; density functional calculations; energy decomposition analysis; molecular geometry; transition-metal complexes; π backdonation