dc.contributor.author |
Van der Westhuizen, Belinda
|
|
dc.contributor.author |
Speck, J. Matthaus
|
|
dc.contributor.author |
Korb, Marcus
|
|
dc.contributor.author |
Friedrich, Joachim
|
|
dc.contributor.author |
Bezuidenhout, Daniela Ina
|
|
dc.contributor.author |
Lang, Heinrich
|
|
dc.date.accessioned |
2014-02-04T13:28:12Z |
|
dc.date.issued |
2013 |
|
dc.description.abstract |
A 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.librarian |
hb2014 |
en_US |
dc.description.sponsorship |
D.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.uri |
http://pubs.acs.org/journal/inocaj |
en_US |
dc.identifier.citation |
Van 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.issn |
0020-1669 (print) |
|
dc.identifier.issn |
1520-510X (online) |
|
dc.identifier.other |
10.1021/ic402202w |
|
dc.identifier.uri |
http://hdl.handle.net/2263/33282 |
|
dc.language.iso |
en |
en_US |
dc.publisher |
American Chemical Society |
en_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.subject |
Spectroelectrochemistry |
en_US |
dc.subject |
Metal-metal interaction |
en_US |
dc.subject |
Ferrocene |
en_US |
dc.subject |
Biferrocene Fischer carbene complexes |
en_US |
dc.title |
Metal–metal interaction in Fischer carbene complexes : a study of ferrocenyl and biferrocenyl tungsten alkylidene complexes |
en_US |
dc.type |
Postprint Article |
en_US |