Reactions of the hydridethiolate complexes [MH(SC6H2R3-2,4,6)3(PMe2Ph)2](M = Mo or W, R = Me or Pri): X-ray crystal structures of [M(SC6H2Pri3-2,4,6)2(CO)2(PMe2Ph)2](M = Mo or W)

Abstract

Reaction of the complexes [MH(SC₆H₂R₃-2,4,6)₃(PMe₂Ph)₂]1(M = Mo or W, R = Me or Prⁱ) with neutral ligands L causes phosphine displacement to give the series [MH(SC₆H₂R₃-2,4,6)₃(PMe₂Ph)L]2[L = R′C₅H₄N, P(OR″)₃ or MeCN; R′= H, 2-, 3- or 4-Me, R″= Me or Et]. Deuterido-analogues were also prepared. Reaction with CO caused hydride and thiolate displacement to give the compounds [M(SC₆H₂R₃-2,4,6)₂(CO)₂(PMe₂Ph)₂] which have different geometries depending upon R. The X-ray crystal structure analyses of [M(SC₆H₂Prⁱ₃-2,4,6)₂(CO)₂(PMe₂Ph)₂]3(M = Mo or W) show them to have essentially trigonal prismatic structures with trigonal faces made from C(O), P and S atoms. The structures and fluxional properties of the carbonyl derivatives and of compounds 2 in solution have been studied by NMR spectroscopy. On treatment with ²H₂ at 1 atm, compounds 1 in solution undergo H/²H exchange of the hydride ligand; the reaction is more effective for M = W than for M = Mo.