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1,1′-Bis(diphenylphosphino)ferrocene bridging two mono(cyclopentadienyl) cobalt moieties: synthesis, structure, electrochemistry and DFT studies

Rosa, V., Realista, S., Mourato, A., Abrantes, L. M., Henriques, J., Calhorda, M. J., Avilés, T., Drew, M. G. B. and Félix, V. (2012) 1,1′-Bis(diphenylphosphino)ferrocene bridging two mono(cyclopentadienyl) cobalt moieties: synthesis, structure, electrochemistry and DFT studies. Journal of Organometallic Chemistry, 712. pp. 52-56. ISSN 0022-328X

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To link to this item DOI: 10.1016/j.jorganchem.2012.04.012

Abstract/Summary

Reaction of [Co(eta(5)-C5H5)(CO)(2)], 1, with 1,1'-bis(diphenylphosphino)ferrocene (dppf) yields the new trinuclear complex [Co(eta(5)-C5H5)(CO)](2)(mu-dppf), 2, which was structurally characterised by single crystal X-ray diffraction and showed two Co(eta(5)-C5H5)(CO) moieties covalently linked by a dppf bridge. Electrochemical studies in dichloromethane revealed that both Co(I) and Fe(II) in the precursors were oxidized to Co(II)/Co(III) and Fe(III), respectively. On the other hand, in 2 the two first oxidation waves were assigned to Co, the Fe(II) centre requiring a higher potential than in free dppf. DFT calculations showed that the HOMOs of 2 were localised in the Co fragments, owing to the destabilisation of the Co(eta(5)-C5H5)(CO) orbitals after binding dppf.

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:30366
Uncontrolled Keywords:Cobalt (I) complexes; dppf ligand; Single crystal X-ray diffraction; Electrochemistry; DFT
Publisher:Elsevier

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