Synthesis, structure and electrochemistry of Fischer alkoxy- and aminocarbene complexes of tungsten : the use of DFT to predict and understand oxidation and reduction potentials

dc.contributor.authorLandman, Marile
dc.contributor.authorPretorius, René
dc.contributor.authorBuitendach, Blenerhassitt E.
dc.contributor.authorVan Rooyen, Petrus H.
dc.contributor.authorConradie, Jeanet
dc.date.accessioned2014-05-12T10:57:09Z
dc.date.available2014-10-31T00:20:06Z
dc.date.issued2013-10
dc.description.abstractReactions of Fischer alkoxycarbene complexes [W(CO)5{C(OEt)Ar}], Ar = thienyl (1) or furyl (2), with ethylene diamine lead to the formation of two different reaction products: an aminolysis product (5 or 6) where the ethoxy substituent of the carbene ligand is replaced by the ethylene diamine moiety, as well as a chelated product where aminolysis and substitution of one carbonyl ligand had taken place, yielding 7 or 8. Aminolysis of 1 and 2 with cyclohexyl amine (CHA) produced the aminocarbene complexes 3 (Ar = thienyl) and 4 (Ar = furyl). Complexes 1-8 are electrochemically investigated by means of cyclic voltammetry. The relative shifts in the oxidation and reduction potentials are discussed and related to density functional theory (DFT) calculated energies. DFT calculations further show that the oxidation center is located on the metal and the carbonyl groups, while the reduction center is localized on the carbene moiety and is strongly influenced by the electronic properties of its substituents. Crystal structures of 1-4, 6 and 8 are reported.en_US
dc.description.librarianhb2014en_US
dc.description.sponsorshipNorwegian Supercomputing Program (NOTUR) through a grant of computer time (Grant No. NN4654K) (J.C.), the South African National Research Foundation (J.C.) and the Central Research Fund of the University of the Free State, Bloemfontein (J.C.), and the University of Pretoria (M.L. and P.H.v.R.).en_US
dc.description.urihttp://pubs.acs.org/journal/orgnd7en_US
dc.identifier.citationLandman, M, Pretorius, R, Buitendach, BE, Van Rooyen, PH & Conradie, J 2013, 'Synthesis, structure and electrochemistry of Fischer alkoxy- and aminocarbene complexes of tungsten : the use of DFT to predict and understand oxidation and reduction potentials', Organometallics, vol. 32, no. 19, pp. 5491-5503.en_US
dc.identifier.issn0276-7333 (print)
dc.identifier.issn1520-6041 (online)
dc.identifier.other10.1021/om400778z
dc.identifier.urihttp://hdl.handle.net/2263/39770
dc.language.isoenen_US
dc.publisherAmerican Chemical Societyen_US
dc.rights© 2013 American Chemical Society.This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, after peer review and technical editing by the publisher. To access the final edited and published work see : Organometallics, vol. 32, no. 19, pp. 5491-5503, 2013,. doi : 10.1021/om400778z Organometallics is available online at : http://pubs.acs.org/journal/orgnd7en_US
dc.subjectSynthesisen_US
dc.subjectStructureen_US
dc.subjectElectrochemistry of Fischer alkoxyen_US
dc.subjectAminocarbene complexes of Tungstenen_US
dc.titleSynthesis, structure and electrochemistry of Fischer alkoxy- and aminocarbene complexes of tungsten : the use of DFT to predict and understand oxidation and reduction potentialsen_US
dc.typePostprint Articleen_US

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