Journal of the American Chemical Society, Vol.117, No.1, 495-500, 1995
Relativistic Effects on Bonding in Cationic Transition-Metal-Carbene Complexes - A Density-Functional Study
Nonrelativistic and quasirelativistic density-functional calculations have been performed aimed at investigating structures and bonding in the cationic methylene complexes MCH(2)(+) of nickel, palladium, platinum, iridium, and gold. Relativistic effects on the bond dissociation energies of these complexes amount to +7, +15, +51, -3, and +66 kcal/mol, respectively. The influence of relativity on bond energies is analyzed in detail and discussed in terms of the s-orbital stabilization and d-orbital destabilization. The relativistic contraction of the M(+)-CH2 bond is found to be small for the group 10 metals and iridium but significant for gold.
Keywords:PERTURBATION-THEORY APPROACH;GAS-PHASE;ELECTRONIC-STRUCTURE;GEOMETRIC STRUCTURES;EFFECTIVE POTENTIALS;GRADIENT CORRECTION;REACTION-MECHANISM;ENERGIES;METHANE;IONS