Bonding in titanocenyl complexes containing O,O'-cyclic ligands

摘要

Density functional theory calculations show that the formal 16-electron count of d~0 [Cp_2Ti~(IV)(O,O'-BID)]~(0/1) complexes containing a O,O'-chelated bidentate ligand O,O'-BID of different ring size, is increased via Ti←O π bonding when both the O donor atoms carry a formal negative charge. The Ti←O π bonding occurs by symmetry lowering of the complex by either symmetrical (C_s) or unsymmetrical (C_2) folding of the O,O'-BID ligand round the O..O axis. An NBO analysis confirms the Ti←O π charge transfer via back-bonding.