THE CALCULATION OF BOND-DISSOCIATION ENERGIES OF TRANSITION-METAL COMPLEXES USING ISOSTRUCTURAL REACTIONS

The metal-ligand bond dissociation energies (CO)(n)M-L are theoretical ly predicted at the HF, MP2 and CCSD(T) levels of theory using effecti ve core potentials for the metals for M = Cr, Mo, W, Ni, Pd, Pt and fo r L = CO, NO+, CN-, NC-, CS, SiO, N-2. The bond energies at the HF lev el are too low and the MP2 values are too high, while the CCSD(T) resu lts are in good agreement with experimental data. The bond energies at MP2 show the same trend as the CCSD(T) values and may therefore be us ed for the prediction of relative bond dissociation energies. The abso lute values for the bond energies calculated at MP2 are significantly improved when they are corrected using the energies of isostructural r eactions M(CO)(n) + L--> M(CO)(n-1)L + CO.