Electrochemical behaviour of cobalta-dicarbollide sandwich complexes with different capping units |
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Authors: | Maddalena Corsini Piero Zanello Alexander R. Kudinov Vladimir I. Meshcheryakov Dmitry S. Perekalin Konstantin A. Lyssenko |
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Affiliation: | (1) Dipartimento di Chimica dell’Università di Siena, Via Aldo Moro, 53100 Siena, Italy;(2) A. N. Nesmeyanov Institute of Organoelement Compounds, 28 ul. Vavilova, 119991 Moscow, GSP-1, Russian Federation |
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Abstract: | The redox aptitude of a series of cobalt(III) or cobalt(I) sandwich complexes bearing a charge compensated dicarbollide ligand ([9-L-7,8-C2B9H10]−) as a constant unit and different counterparts (varying from classical [7,8-C2B9H11]2− to charge-compensated [9-L-7,8-C2B9H10]− dicarbollides, from cyclopentadienyl [C5R5]− (R = Me, H) to cyclobutadiene [C4Me4]0 ligands) has been studied. All the Co(III) complexes display the reversible sequence Co(III)/Co(II)/Co(I). In contrast, the Co(I) complexes (namely, those capped by tetramethylcyclobutadiene) accede reversibly only to the Co(II) oxidation state, the passage to Co(III) being irreversible. When possible, the Co(II) intermediates have been characterized by EPR spectroscopy. The molecular structures of the monocation [Co(η-9-SMe2-7,8-C2B9H10)2]+ in its DD/LL and meso diastereomeric forms as well as that of heteroleptic (η-7,8-C2B9H11)Co(η-9-SMe2-7,8-C2B9H10) have been obtained by single-crystal diffraction. Presented at the 3rd Chianti Electrochemistry Meetings July 3−9, 2004, Certosa di Pontignano, Italy |
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