Abstract
Coordinate bond nature and stereochemistry of several group VIII transition metal complexes have been successfully investigated with ab-initio MO method and energy decomposition analysis (EDA). Ni(PH3)2(CO)2 takes pseudo-tetrahedral (p-Td) structure, to avoid large exchange repulsion between the Ni d and the CO lone-pair orbitals. On the other hand, Ni(PH3)3 (H2CO) has planar (PI) structure, because of strong back-donative interaction in this structure. In RhCl(PH3)2(N2), the n1-end on mode receives larger stabilization from the N2→ Rh donative interaction and the electrostatic interaction between N2 and Rh than the η2-side on mode does, and as a result, the η1 -end on mode is more stable than the η2-side on mode. Several coordination modes are also examined in CO2 complexes. The η2-side on mode is stable in Ni(PH3)2(CO2), because large back-donative (M dπ→CO2 π*) interaction is possible. The strong (M dπ→CO2 π*) back-donative interaction favors the η1-C mode in [Co(alcn)2(CO2)]− (alcn = NHCH-CH-OH-O−)The electrostatic interaction is important in the η1-O end on mode, and this mode is most stable in [Cu(PH3)2(CO2)]+.
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Sakaki, S. (1986). Stereochemistry and Metal-ligand Interaction of Group VIII Low-Valent Transition Metal Complexes. An ab-initio MO and Energy Decomposition Analysis Study. In: Veillard, A. (eds) Quantum Chemistry: The Challenge of Transition Metals and Coordination Chemistry. NATO ASI Series, vol 176. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-4656-9_22
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DOI: https://doi.org/10.1007/978-94-009-4656-9_22
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