0181556 - UFCH-W 20020188 RIV GB eng J - Journal Article
Fiedler, Jan - Nervi, C. - Osella, D. - Calhorda, M. J. - Godinho, S. M. C. - Merkel, R. - Wadepohl, H.
Electrochemical Behaviour, IR Spectroelectrochemistry and Theoretical Studies of Tetracobalt Carbonyl Cluster Complexes with a Facial Cyclooctatetraene Ligand.
Journal of the Chemical Society. Dalton Transactions. - (2002), s. 3705-3711. ISSN 1472-7773
R&D Projects: GA MŠMT OC D15.10
Institutional research plan: CEZ:AV0Z4040901
Keywords : spectroelectrochemistry * electron-transfer reactions
Subject RIV: CG - Electrochemistry
Impact factor: 3.023, year: 2002

The redox properties of some cluster complexes with a facial cyclooctatetraene (cot) ligand were investigated using electrochemical and IR spectroelectrochemical techniques. Reduction of [Co-4 (CO)(3) (eta(3)-CO)(3) (mu(3)-C8H8)L-2] 1 (L-2 = eta(4) -C8H8), 2 (L-2 = eta(4)-C6H8), and 3 (L-2 = eta(4) -6,6-Ph2C6H4) occurs in CH2Cl2 or THF solution in two consecutive one-electron electrochemically reversible steps. Both one- and two-electron primary reduction products are unstable on a longer timescale; eventually degradation (decapitation) of the tetranuclear clusters takes place, to give the stable anion [Co-3 (CO)(3) (mu-CO)(3) (mu(3)-C8H8)](-) 5. The electronic structure of 1, 2, the octacarbonyl derivative [Co-4 (CO)(5) ( mu(3)-CO)(3) (mu(3)-C8H8)] 4, their monoanions, dianions and 5 was investigated using ab initio DFT MO calculations.
Permanent Link: http://hdl.handle.net/11104/0078107