title: Mono-oxo bis(dithiolene) Mo(IV)/W(IV) complexes as building blocks for sulfide bridged Bi- and Tri-nuclear complexes.
abstract: A new electron precise, six-electron, sulfide-bicapped trinuclear cluster complex [Et4N]4[Mo(IV)3(mu3-S)2(mnt)6] (1) has been synthesized, where each Mo(IV) atom is seven coordinated. Identical reaction conditions yielded a dimeric complex, [PNP]2[W(V)2(mu2-S)2(mnt)4] (2) from the starting W(IV) analogue due to oxidation by sulfur formed by the auto-oxidation of H2S. Two stepwise reversible reductions and no oxidation of 2 as observed by cyclic voltammetry are correlated with the nonbonding nature of the lowest unoccupied molecular orbital and deeply buried highest occupied molecular orbital by theoretical calculations at the density-functional theory level.
authors.affiliation: Indian Institute of Technology, Kanpur, Kanpur, Uttar Pradesh, India.
authors.forename: Amit
authors.initials: A
authors.lastname: Majumdar
authors.forename: Joyee
authors.initials: J
authors.lastname: Mitra
authors.forename: Kuntal
authors.initials: K
authors.lastname: Pal
authors.forename: Sabyasachi
authors.initials: S
authors.lastname: Sarkar