Preparation and Some Properties of [CoIIorIII{RhIII(aet or l-cys-N,S)3}2]-Type S-Bridged Trinuclear Complexes
- 1 March 1990
- journal article
- research article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 63 (3) , 792-798
- https://doi.org/10.1246/bcsj.63.792
Abstract
The reactions of fac-[Rh(aet)3] (aet=2-aminoethanethiolate) or ΔLLL-fac-[Rh(L-cys-N,S)3]3− (L-cys=L-cysteinate) with [CoCl(NH3)5]2+ produced [CoIII{RhIII(aet or L-cys-N,S)3}2]3+or3−, while the reactions with Co2+ formed [CoII{RhIII(aet or L-cys-N,S)3}2]2+or4− which were oxidized to give [CoIII{RhIII (aet or L-cys-N,S)3}2]3+or3−. These complexes were optically resolved or separated by fractional crystallization or column chromatography, and characterized from their absorption, CD and 13C NMR spectra. The reactions of fac-ΔLLL-[Rh(L-cys-N,S)3]3− with [CoCl(NH3)5]2+ or Co2+ at room temperature proceeded with retention of the starting ΔLLL configuration to give the ΔLLLΔLLL isomer, while the reaction with Co2+ at high temperature (ca. 95 °C) was accompanied by inversion to form the ΔLLLΛLLL, ΛLLLΛLLL, and ΔLLLΔLLL isomers. Cyclic voltammetric measurements of [CoIII {RhIII(aet or L-cys-N,S)3}2]3+or3− in water showed a quasi-reversible redox couple corresponding to the central Co(III)/(II) at ca. −0.3 V vs. Ag/AgCl. Their absorption and CD spectra and cyclic voltammograms are discussed in comparison with those of the corresponding [CoIII{CoIII (aet or L-cys-N,S)3}2]3+or3−.Keywords
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