Stereochemistry and Metal-ligand Interaction of Group VIII Low-Valent Transition Metal Complexes. An ab-initio MO and Energy Decomposition Analysis Study

摘要: Coordinate bond nature and stereochemistry of several group VIII transition metal complexes have been successfully investigated with ab-initio MO method energy decomposition analysis (EDA). Ni(PH3)2(CO)2 takes pseudo-tetrahedral (p-Td) structure, to avoid large exchange repulsion between the Ni d CO lone-pair orbitals. On other hand, Ni(PH3)3 (H2CO) has planar (PI) because strong back-donative interaction in this structure. In RhCl(PH3)2(N2), n1-end on mode receives larger stabilization from N2→ Rh donative electrostatic N2 than η2-side does, as a result, η1 -end is more stable mode. Several coordination modes are also examined CO2 complexes. The Ni(PH3)2(CO2), (M dπ→CO2 π*) possible. favors η1-C [Co(alcn)2(CO2)]− (alcn = NHCH-CH-OH-O−)The important η1-O end mode, most [Cu(PH3)2(CO2)]+.