Structure and Bonding of the Transition-Metal Carbonyl Complexes M(CO)5L (M = Cr, Mo, W) and M(CO)3L (M = Ni, Pd, Pt; L = CO, SiO, CS, N2, NO+, CN-, NC-, HCCH, CCH2, CH2, CF2, H2)1

Abstract

Quantum mechanical ab initio calculations at the MP2 and CCSD(T) level of theory using effective core potentials (ECP) for the metals with a valence basis set of DZP quality and a 6-31G(d) all-electron basis set for the other elements are reported for the complexes M(CO) 5 L (M = Cr, Mo, W) and M(CO) 3 L (M = Ni, Pd, Pt) with ligands L = CO, SiO, CS, N 2, NO +, CN -, NC -, HCCH, CCH 2, CH 2, CF 2, and H 2 . The optimized geometries at MP2/II are in very good agreement with experiment. The theoretically predicted (CO) n M−L bond dissociation energies at CCSD(T)/II using MP2/II optimized geometries also agree quite well with experimental data. The (CO) n M−L bond is investigated using the charge decomposition analysis (CDA), which gives an interpretation of the donor−acceptor complexes in terms of charge donation, back-donation and repulsive polarization. The CDA results, which may be considered as a quantitative expression of the Dewar−Chatt−Duncanson model, are in agreement with the standard classification of the ligands.