Electrochemical behaviour and structure of novel phosphine- and phosphite-substituted tungsten(0) Fischer carbene complexes

dc.contributor.authorLandman, Marile
dc.contributor.authorPretorius, René
dc.contributor.authorFraser, Roan
dc.contributor.authorBuitendach, Blenerhassit E.
dc.contributor.authorConradie, Marrigje M.
dc.contributor.authorVan Rooyen, Petrus H.
dc.contributor.authorConradie, Jeanet
dc.contributor.emailmarile.landman@up.ac.zaen_ZA
dc.date.accessioned2015-03-09T12:24:30Z
dc.date.available2015-03-09T12:24:30Z
dc.date.issued2014-06
dc.description.abstracttThe electrochemical behaviour of a series of sixteen novel Fischer ethoxy- and aminocarbenecomplexes of the type [(CO)4(PPh3)W = C(X)R] with R = 2-thienyl or 2-furyl and X = OEt or NHCy,(1-4), [(CO)3(dppe)W = C(X)R] with R = 2-thienyl or 2-furyl and X = OEt or NHCy, (5-8) (dppe = 1,2-bis(diphenylphosphino)ethane) and [(CO)4P(OPh)3W = C(X)R] with R = 2-thienyl or 2-furyl and X = OEtor NHCy, (9-12) is investigated by means of cyclic voltammetry. The complexes all exhibit a two-electronoxidation process that is W-based and a one-electron reduction that is mainly localized on the carbeneligand. Complexes 1-4 and 9-12 are considerably more difficult to oxidize than 5-8 due to the better -acceptor ability of the (CO)4(PR 3) (R = Ph or OPh) ligand combination than that of (CO)3(dppe). Den-sity functional theory calculations on the neutral, reduced and oxidized complexes confirmed the role ofthe frontier orbitals in the oxidation and reduction processes and enabled formulation of mathematicalrelationships that can be used to predict experimental measured potentials. X-ray crystal structures of2cis, 3 and 5 are discussed.en_ZA
dc.description.librarianhb2015en_ZA
dc.description.urihttp://www.elsevier.com/locate/electactaen_ZA
dc.identifier.citationLandman, M, Pretorius, R, Fraser, R, Buitendach, BE, Conradie, MM, Van Rooyen, PH & Conradie, J 2014, 'Electrochemical behaviour and structure of novel phosphine- and phosphite-substituted tungsten(0) Fischer carbene complexes', Electrochimica Acta, vol. 130, pp. 104-118.en_ZA
dc.identifier.issn0013-4686 (print)
dc.identifier.issn1873-3859 (online)
dc.identifier.other10.1016/j.electacta.2014.02.127
dc.identifier.urihttp://hdl.handle.net/2263/43897
dc.language.isoenen_ZA
dc.publisherElsevieren_ZA
dc.rights© 2014 Published by Elsevier Ltd. All rights reserved. Notice : this is the author’s version of a work that was accepted for publication in Electrochimica Acta. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Electrochimica Acta, vol. 130, pp.104-118, 2014. doi : 10.1016/j.electacta.2014.02.127en_ZA
dc.subjectFischer carbeneen_ZA
dc.subjectTungstenen_ZA
dc.subjectPhosphineen_ZA
dc.subjectElectrochemistryen_ZA
dc.subjectDensity functional theory (DFT)en_ZA
dc.titleElectrochemical behaviour and structure of novel phosphine- and phosphite-substituted tungsten(0) Fischer carbene complexesen_ZA
dc.typePostprint Articleen_ZA

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