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.

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
• Electronic ISSN: 1873-3255
• Publisher: Elsevier
• Peer Reviewed: Peer Reviewed
• Volume: 380
• Pages: 358-371
• DOI: https://doi.org/10.1016/j.ica.2011.10.067
• Public URL: https://durham-repository.worktribe.com/output/1455074