Abstract
Studies of electric dipole moments, electric birefringences, carbonyl infrared frequencies and interatomic bond distances provide mutually reinforcing evidence for π-acid behaviour of the bicyclic phosphite ligand in [M(CO)5{P(OCH2)3CMe}] complexes (M = Cr, Mo or W). Molecular optical anisotropies and directional polarisabilities from experiment are analysed to show strong polarisability enhancement along the molecular symmetry axis and concomitant diminution of polarisability perpendicular to that axis, relative to a hypothetical σ-bonded P–M model. The results provide evidence for a highly deformable π-component in the phosphorus–metal bonding and for a π-delocalised P–M–CO(trans) system. Comparisons are made with other [M(CO)5L] compounds where L = quinuclidine, PMe3 or PCl3. The crystal structure of [Mo(CO)5{P(OCH2)3CMe}] is reported and bond dimensions are compared with those of related molybdenum complexes.
Published Version
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