resumo
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. (C) 2012 Elsevier B.V. All rights reserved.
palavras-chave
SUPERCRITICAL CARBON-DIOXIDE; POLARIZABLE CONTINUUM MODEL; MOLECULAR-ORBITAL METHODS; GAUSSIAN-TYPE BASIS; CRYSTAL-STRUCTURE; ORGANIC-MOLECULES; SOLVATION MODELS; BASIS-SETS; AB-INITIO; COMPLEXES
categoria
Chemistry
autores
Rosa, V; Realista, S; Mourato, A; Abrantes, LM; Henriques, J; Calhorda, MJ; Aviles, T; Drew, MGB; Felix, V
nossos autores
Vítor Félix
Professor Associado com Agregaçãoagradecimentos
We thank Fundacao para Ciencia e Tecnologia for financial support: grant PEst-C/EQB/LA0006/2011, PEst-OE/QUI/UI0612/2011, Project PTDC/QUI-QUI/099873/2008, co-financed by FEDER, and fellowships to V.R. (SFRH/BPD/44262/2008) and A.M. (SFRH/BPD/35036/2007).