Abstract
Quantum mechanical ab initio calculations using effective core potentials (ECPs) of the geometries and bond dissociation energies of transition-metal carbonyl complexes containing H2O, NH3 and PH3 are discussed≪ The geometries are optimized at the MP2 level of theory using valence basis sets of DZ+P quality. The bond dissociation energies are predicted at the CCSD(T) level of theory. The theoretical data are generally in good agreement with experimental values. The metal-ligand interactions are analyzed using the topological analyis of the charge distribution, the natural bond orbital (NBO) partitioning scheme and the charge decomposition analysis (CDA) based upon fragment molecular orbitals. H2o and NH3 are pure σ donors which are mainly bound through coulombic interactions. The metal-PH3 bonds have covalent contributions and show metal→3 π-backdonation, which is weaker than in CO, however.
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Frenking, G., Dapprich, S., Meisterknecht, T., Uddin, J. (2000). Structure and Bonding of M(CO)3(H2O), M(CO)5(NH3), and M(CO)5(PH3) (M = Cr, Mo, W)1 . In: Russo, N., Salahub, D.R. (eds) Metal-Ligand Interactions in Chemistry, Physics and Biology. NATO Science Series, vol 546. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-4245-8_4
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