5-CO-ORDINATE COMPLEXES [MOH(SC(6)H(2)R(3)-2,4,6)(3)(PR'PH(2))] (R=ME OR PR(I), R'=ME OR ET) AND THEIR REACTIONS WITH NITROGEN DONORS - CRYSTAL-STRUCTURES OF [MOH(SC(6)H(2)PR(I)(3)-2,4,6)(3)(C(5)H(5)N)(PME(2)PH)] AND [PPH(4)][MOO(SC(6)H(2)PR(I)(3)-2,4,6)(4)]

The complexes [MoH(SC6H2R3-2,4,6)3(PR'Ph2)] 1 (R = Me or Pr(i), R' = Me or Et) have been prepared by reaction of HSC6H2R3-2,4,6 with [MoH4(PR'Ph2)4] or trans-[Mo(N2)2(PR'Ph2)4]. Compound 1 (R = Pr(i), R' = Me) reacted with N-donor ligands L (C5H5N, 3,5-Me2C5H3N or C3H3NS) to give the adducts 2, [MoH(SC6H2Pr(i)3-2,4,6)3L(PMePh2)]. The crystal structure of the analogue [MoH(SC6H2Pr(i)3-2,4,6)3(C5H5N)(PMe2Ph)] showed the compound to have a trigonal girdle of thiolate ligands with the pyridine and PMe2Ph ligands in essentially apical positions. Reaction of 1 (R = Pr(i), R' = Et) with NC5H4SH-2 gave the seven-co-ordinate complex [MoH(SC6H2Pr(i)3-2,4,6)(NC5H4S-2)2-(PEtPh2)], shown by X-ray crystallography to have an essentially pentagonal-pyramidal geometry with the hydride located in the equatorial plane. Spectroscopic data for the compounds are discussed in terms of their structures. Complex 1 (R = Pr(i), R' = Et) exchanges hydride for deuteride on treatment with deuterium gas in benzene at 20-degrees-C. Treatment of 1 (R = Pr(i), R' = Me) in Me) in MeOH with LiBEt3H, followed by [PPh4]Cl, gave [PPh4][MoO(SC6H2Pr(i)3-2,4,6)4], shown by X-ray crystallography to have an anion with square-pyramidal geometry and an apical oxide-ligand.