Molecular structure, bonding, and reaction of Mo(η5-C5H5)2 derivatives containing phosphorus ligands. Crystal structures of 5-C5H5)2H(PPh3)>I*1/2H2O and 5-C5H5)2(CH3)(PPh3)>

Article abstract of DOI:10.1016/0022-328X(90)85060-C

The oxidative addition reactions of 5-C5H5)2(PPh3)>, prepared by deprotonation of 5-C5H5)2H(PPh3)> with HCl, CH3I, (CH3)3SiCl and (C2H5)2S2 are described.Two of the complexes obtained have been characterized by single crystal X-ray diffraction studies, viz: 2-C5H5)2H(PPh3)>I.1/2H2O (1a) and 5-C5H5)2(CH3)(PPh3)> (3).In complex 1a, the Mo-H and Mo-P bond lengths are 1.74(8) and 2.501(4) Angstroem, and the H-Mo-P angle is 77(2) deg, while in complex 3 the Mo-C and Mo-P bond lengths are 2.269(7) and 2.526(4) Angstroem and the C-Mo-P angle is 84.1(2) deg.Molecular orbital and steric energy calculations have been carried out for some model complexes in order to throw light on their geometrical preferences and to evaluate the influence of a bulky ligand in association with a small hydride on the overall geometry of the molecule.