The synthesis, molecular and electronic structure of cyanovinylidene complexes

Long, Ella M.; Brown, Neil J.; Man, Wing Y.; Fox, Mark A.; Yufit, Dmitry S.; Howard, Judith A.K.; Low, Paul J.

doi:10.1016/j.ica.2011.10.067

The synthesis, molecular and electronic structure of cyanovinylidene complexes

Long, Ella M.; Brown, Neil J.; Man, Wing Y.; Fox, Mark A.; Yufit, Dmitry S.; Howard, Judith A.K.; Low, Paul J.

Authors

Ella M. Long

Neil J. Brown

Wing Y. Man

Dr Mark Fox m.a.fox@durham.ac.uk
Assistant Professor

Dmitry S. Yufit

Judith A.K. Howard

Paul J. Low

Abstract

Reaction of the readily available metal acetylide complexes Ru(CCC6H4R-4)(PPh3)2Cp (R = OMe, Me, H, CN, CO2Me), Ru(CCFc)(PPh3)2Cp and Fe(CCC6H4R-4)(dppe)Cp (R = Me, H) with 1-cyano-4-dimethylaminopyridinium tetrafluoroborate affords cyanovinylidene complexes [Ru{CC(CN)C6H4R-4}(PPh3)2Cp]BF4, [Ru{CC(CN)Fc}(PPh3)2Cp]BF4 and [Fe{CC(CN)C6H4R-4}(dppe)Cp]BF4 in an experimentally simple fashion. These synthetic studies are augmented by refinements to the preparation of the key iron reagents FeCl(dppe)Cp and Fe(CCC6H4R-4)(dppe)Cp. Molecular structure determinations, electrochemical measurements, representative IR spectroelectrochemical studies and DFT studies have been used to provide insight into the electronic structure of the cyanovinylidene ligand, and demonstrate that despite the presence of the cyano-substituted methylidene fragment, reduction takes place on the vinylidene Cα carbon.

Citation

Long, E. M., Brown, N. J., Man, W. Y., Fox, M. A., Yufit, D. S., Howard, J. A., & Low, P. J. (2012). The synthesis, molecular and electronic structure of cyanovinylidene complexes. Inorganica Chimica Acta, 380, 358-371. https://doi.org/10.1016/j.ica.2011.10.067

Journal Article Type	Article
Publication Date	Jan 1, 2012
Deposit Date	May 2, 2013
Publicly Available Date	Aug 15, 2013
Journal	Inorganica Chimica Acta
Print ISSN	0020-1693
Publisher	Elsevier
Peer Reviewed	Peer Reviewed
Volume	380
Pages	358-371
DOI	https://doi.org/10.1016/j.ica.2011.10.067

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Copyright Statement
NOTICE: this is the author’s version of a work that was accepted for publication in 'Inorganica Chimica 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 Inorganica Chimica Acta., 380, 2012, 10.1016/j.ica.2011.10.067