Caldwell, Lorraine M.Hill, Anthony F.Stranger, RobertTerrett, Richard N. L.von Nessi, Kassetra M.Ward, Jas S.Willis, Anthony C.2015-06-022015-06-020276-7333http://hdl.handle.net/1885/13701The reaction of [Mo(≡CBr)(CO)2(Tp*)] (Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with [Fe2(μ-SLi)2(CO)6] affords, inter alia, the unsymmetrical binuclear thioxoethenylidene complex [Mo2(μ,σ(C):η2(C′S)-CCS)(CO)4(Tp*)2], which may be more directly obtained from [Mo(≡CBr)(CO)2(Tp*)] and Li2S. The reaction presumably proceeds via the intermediacy of the bis(alkylidynyl)thioether complex S{C≡Mo(CO)2(Tp*)}2, which was, however, not directly observed but explored computationally and found to lie 78.6 kJ mol–1 higher in energy than the final thioxoethenylidene product. Computational interrogation of the molecules [M2(μ-C2S)(CO)2(Tp*)2] (M = Mo, W, Re, Os) reveals three plausible coordination modes for a thioxoethenylidene bridge which involve a progressive strengthening of the C–C bond and weakening of the M–C and M–S bonds, as might be expected from simple effective atomic number considerations.This work was supported by the Australian Research Council (DP130102598 and DP110101611).7 pages© 2014 American Chemical Society. http://www.sherpa.ac.uk/romeo/issn/0276-7333/ Author can archive post-print (ie final draft post-refereeing), after 12 months embargo (Sherpa/Romeo as of 30/8/2017)ReactionAtomsMolybdenumUnsymmetrical binuclear thioxoethenylidene complexRheniumTungstenBridging ligandsC-C bondsCBrCoordination modesEffective atomic numberThioether complexesMolybdenum compounds2015-01-1210.1021/om50113192015-12-10