An Ab Initio Study on the Coordination of Formaldehyde, Carbon Dioxide, Dinitrogen, and Related Molecules to Iron(0) and Nickel(0) Fragments
‘Ab initio’ calculations have been performed on the model systems Fe(CO) n (PH 3)4-n (η 2 - L) L = CH 2 O, CH 2 S, CMe 2 O; n = 0, 2, 4; Fe(CO)2(PH 3)2(η 2 - OCX), Fe(CO)2(PH 3)2 (η 2 - SCX), X = O, S, NH, CH 2; Fe(PH3)4(N2), Ni(PH 3)2(L), L = N 2, N 2 CH 2, N 2 H 2; to investigate the nature and the energetics of the interaction between the metal and the unsaturated ligand. The results allow a complete description of the electronic structure of the model compounds: the bonding between the metallic fragment and the unsaturated molecule lies at the very extreme of the Chatt-Dewar-Duncanson model, being dominated by the π-back-donation. The coordinate bond of CH 2 O with an iron(0) substrate and that of N 2 with a nickel(0) fragment are described in details, paying particular attention to the role of correlation effects.
KeywordsBinding Energy Coordinate Bond Configuration Interaction Effective Bonding Distortion Angle
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