[MoBr2(CO)4] reacts with 2,4,6-Pri3C6H2S- (TIPT-) to give trigonal bipyramidal [Mo(CO)2(TIPT)3]- (I). The tungsten and rhenium analogues are isostructural. Complex I reacts with neutral donors to give [Mo(TIPT)3(CO)L]- (L = MeCN, ButCN, MeNC, ButNC or PMe2Ph) and with [PhN2][BF4] to give [Mo(N2Ph)(TIPT)3(MeCN)] (II). Complex II is also trigonal bipyramidal with axial N2Ph and MeCN ligands. [MoCl3(MeCN)3] reacts with TIPT in MeCN to give "[Mo(MeCN)(TIPT)4]". By contrast, MoCl4 in dimethoxyethane with TIPT gives [Mo2(TIPT)6] together with [MoO(TIPT)4]-. An X-ray crystal structure of [Mo2(TIPT)6] revealed an Mo-Mo triple bond analogous to [Mo2(OR)6] species. The phenylated thiol, 2,6-Ph2C6H3S-), reacts with [MoBr2(CO)4] in dimethoxyethane to give [Mo(CO)(DPT)2]. One of the o-phenyl groups is η6-bonded to give a distorted piano-stool structure. The η6-phenyl group is readily displaced by a range of neutral donor ligands to give access to a new series of Mo(II) thiolato-derivatives.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry