THE REACTIONS OF DECACARBONYLDIRHENIUM WITH SOME ORGANO-PHOSPHANES AND PHOSPHITES

Article abstract of DOI:10.1016/S0022-328X(00)82415-8

The reactions between Re2(CO)10 and a number of organo-phosphanes and phosphites in refluxing xylene have been studied.With P(OPh)3, the products are 1,2-diaxial-Re2(CO)8L2 and 1-axial-2,2'-axial,equatorial-Re2(CO)7L3, whereas with (o-CH3C6H4O)3P, 1,2-diaxial-Re2(CO)8L2 and the metalated complex Re(CO)3L(L-H) are formed.In the case of (p-ClC6H4O)3P, only 1,2-diaxial-Re2(CO)8L2 was isolated. (p-CH3C6H4)3P and (cyclohexyl)3P both yield 1,2-diaxial-Re2(CO)8L2 and mer-trans-HRe(CO)3L2, however, (o-CH3C6H4)3P gives only the metalated product, Re(CO)4L-H.Formation of the hydrides and metalated compounds is rationalised in terms of the homolysis of the metal-metal bonded dimers to yield metal-centred free radical intermediates.The behaviour of the dimers and the radical intermediates is discussed in terms of the properties of the phosphorus donor ligands.