Metal–metal interaction in Fischer carbene complexes : a study of ferrocenyl and biferrocenyl tungsten alkylidene complexes

dc.contributor.authorVan der Westhuizen, Belinda
dc.contributor.authorSpeck, J. Matthaus
dc.contributor.authorKorb, Marcus
dc.contributor.authorFriedrich, Joachim
dc.contributor.authorBezuidenhout, Daniela Ina
dc.contributor.authorLang, Heinrich
dc.contributor.emaildaniela.bezuidenhout@up.ac.zaen_US
dc.date.accessioned2014-02-04T13:28:12Z
dc.date.issued2013
dc.description.abstractA series of ferrocenyl (Fc = ferrocenyl; fc = ferrocen-1,1'-diyl) and biferrocenyl (Bfc = 1',1''-biferrocenyl; bfc = 1',1''-biferrocen-1,1'''-diyl) mono- and biscarbene tungsten(0) complexes of the type [(CO)5W=C(OMe)R] (1, R = Fc; 3, R = Bfc) and [(CO)5W=C(OMe)-R'-(OMe)C=W(CO)5] (2, R' = fc; 4, R' = bfc) were synthesized according to the classical synthetic methodology by reacting W(CO)6 with LiR (R = Fc, fc, bfc), followed by a subsequent alkylation using methyl trifluoromethanesulfonate. Electrochemical investigations were carried out on these complexes to get a closer insight into the electronic properties of 1 - 4. The ferrocenyl and biferrocenyl moieties in 1 – 4 show reversible one electron redox events. It was further found that the Fischer carbene unit is reducible in an electrochemical one electron transfer process. For the tungsten carbonyl moieties, irreversible oxidation processes were found. In addition, charge transfer studies were performed on 1 - 4 by the use of in situ UV-Vis-NIR and infrared spectroelectrochemical techniques. During the UV-Vis-NIR investigations typical low energy transitions for the mixed-valent biferrocenyl unit were found. A further observed high energy NIR absorption is attributed to a metal-metal charge transfer transition between the tungsten carbonyl fragment and the ferrocenyl/biferrocenyl group in the corresponding oxidized states, which can be described as class II systems according to Robin and Day. This assignment was verified by infrared spectroelectrochemical studies. The electrochemical investigations are supported by DFT calculations. The structural properties of 1 - 4 in the solid state were investigated by single-crystal Xray diffraction studies showing no substituent effects on bond lengths and angles. The biferrocenyl derivatives exhibit synconformation of the ferrocenyl and carbene building blocks.en_US
dc.description.librarianhb2014en_US
dc.description.sponsorshipD.I.B. and B.v.d.W. acknowledge the National Research Foundation, South Africa for financial support (Grant number 76226). We are grateful to the Fonds der Chemischen Industrie for financial support. J.M.S. and M.K. thank the FCI for Chemiefonds Fellowships.en_US
dc.description.urihttp://pubs.acs.org/journal/inocajen_US
dc.identifier.citationVan der Westhuizen, B, Speck, JM, Korb, M, Friedrich, J, Bezuidenhout, DI & Lang, H 2013,'Metal–metal interaction in Fischer carbene complexes : a study of ferrocenyl and biferrocenyl tungsten alkylidene complexes', Inorganic Chemistry, vol.52, no. 24, pp.14253-14263.en_US
dc.identifier.issn0020-1669 (print)
dc.identifier.issn1520-510X (online)
dc.identifier.other10.1021/ic402202w
dc.identifier.urihttp://hdl.handle.net/2263/33282
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 Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see : http://pubs.acs.org/journal/inocaj.en_US
dc.subjectSpectroelectrochemistryen_US
dc.subjectMetal-metal interactionen_US
dc.subjectFerroceneen_US
dc.subjectBiferrocene Fischer carbene complexesen_US
dc.titleMetal–metal interaction in Fischer carbene complexes : a study of ferrocenyl and biferrocenyl tungsten alkylidene complexesen_US
dc.typePostprint Articleen_US

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