SYNTHESES AND STRUCTURES OF [RE(SC(6)H(3)ME(2)-2,6)(3)(PPH(3))], [RE(SC(6)H(3)ME(2)-2,6)(3)(BU(T)NC)(2)], [RE(SC6H2PR3I-2,4,6)(3)L(PPH(3))] (L=N-2 OR CO) AND [REH4(PPH(3))(4)] [REO(SC6H2PR3I-2,4,6)(4)]

The hydride [ReH7(PPh(3))(2)] reacted with 2,6-dimethylbenzenethiol in toluene to give a complex of stoichiometry [Re(SC(6)H(3)Me(2)-2,6)(3)(PPh(3))] 1. A crystal structure showed a trigonal-bipyramidal geometry about the Re with Bn agostic interaction to a thiolate methyl occupying an apical site. trans to the PPh(3) ligand. Complex 1 reacts rapidly with MeCN to give the known [Re(SC(6)H(3)Me(2)-2,6)(3)(MeCN)(PPh(3))] 2 and with Bu(dagger)NC to form [Re(SC(6)H(3)Me(2)-2,6)(3)(Bu(t)NC)(2)]. 3 The crystal structure of 3 showed trigonal-pyramidal geometry about the Re with asymmetric co-ordination of the isocyanide ligands and an unusual configuration for the thiolate aromatic groups; The reactions of the hydrides [ReH7(PPh(3))(2)] and [ReH5(PPh(3))(3)] with 2,4,6-triisopropyl-. 2.6-dimethdxy-benzenethiol and tris(2-sulfanylphenyl)phosphine were also studied. With HSC6H2Pr3i-2,4,6 the dinitrogen complex [Re(SC6H2Pr3i-2,4,6)(3)(N-2)(PPh(3))] 4 was formed and its structure determined. The preparations and structures of the complexes [ReH4(PPh(3))(4)][ReO(SC6H2Pr3i-2,4,6)(4)], [Re{SC6H3(OMe)(2)-2,6}(3)(PPh(3))] and [Re{P(C6H4S-2)(3)}(PPh(3))] are also discussed. An alternative convenient route to [ReH4(PPh(3))(4)](+) from [ReH5(PPh(3))(3)] is presented.