Molecular orbital calculations on transition metal complexes. Part II. Hexa-aquometal(II) and hexa-aquometal(III) ions

Abstract

CNDO Molecular orbital calculations are reported for hexa-aquometal(II) complexes (Ti^II—Cu^II) and hexa-aquometal(III) complexes (Ti^III—Co^III). The mechanism for spin delocalisation in these complex ions is discussed and the CNDO results suggest that an approximately tetrahedral geometrical configuration around the oxygen atoms is evident. In general it is found that equilibrium bond lengths are not well predicted; however the ions Cu^II(H₂O)₆, Cr^II(H₂O)₆, and Mn^III(H₂O)₆, which have orbitally degenerate ground states, are predicted to undergo a distortion of the Jahn–Teller type. Electronic configurations, covalency, and charge effects are also discussed.