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Diphosphine Mobility at a Binuclear Metal Center: A Concerted Double Trigonal-Twist in Bis(dithiolate) Complexes [M-2(CO)(4)(mu-dppm){mu-S(CH2)(n)S}] (M = Fe, Ru; n=2, 3)

Hogarth, G; Kabir, SE; Richards, I; (2010) Diphosphine Mobility at a Binuclear Metal Center: A Concerted Double Trigonal-Twist in Bis(dithiolate) Complexes [M-2(CO)(4)(mu-dppm){mu-S(CH2)(n)S}] (M = Fe, Ru; n=2, 3). ORGANOMETALLICS , 29 (23) 6559 - 6568. 10.1021/om100894w.

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Abstract

Heating [M-2(CO)(6){mu-S(CH2)(n)S}] (M = Fe, Ru; n = 2 (edt), 3 (pdt)) with bis(diphenylphosphino)methane (dppm) in toluene affords the bridged-diphosphine complexes [M-2(CO)(4)(mu-dppm){mu-S(CH2)(n)S}]. At room temperature, all show two separate environments for the methylene protons of the diphosphine ligand, while at higher temperatures these coalesce to a single peak. This behavior, which interconverts the two sulfur atoms, is ascribed to a concerted double trigonal-twist of the M(CO)(2)P moieties. No such fluxional behavior was observed for the nonlinked dithiolate complexes [Fe-2(CO)(4)(mu-dppm)(mu-SR)(2)] (R = Me, Ph, p-tolyl). The X-ray structures of [M-2(CO)(4)(mu-dppm)(mu-edt)] (M = Fe, Ru) and [Fe-2(CO)(4)(mu-dppm)(mu-SMe)(2)] are presented in order to compare them to the previously reported [M-2(CO)(4)(mu-dppm)(mu-pdt)].

Type:Article
Title:Diphosphine Mobility at a Binuclear Metal Center: A Concerted Double Trigonal-Twist in Bis(dithiolate) Complexes [M-2(CO)(4)(mu-dppm){mu-S(CH2)(n)S}] (M = Fe, Ru; n=2, 3)
DOI:10.1021/om100894w
Keywords:IRON-ONLY HYDROGENASE, X-RAY STRUCTURES, HETEROCYCLIC CARBENE LIGANDS, ACTIVE-SITE MODELS, CLOSTRIDIUM-PASTEURIANUM, DITHIOLATE COMPLEXES, EXCHANGE PROCESSES, FUNCTIONAL MODELS, CRYSTAL-STRUCTURE, DIIRON COMPLEXES
UCL classification:UCL > School of BEAMS > Faculty of Maths and Physical Sciences > Chemistry

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