S-bridged polynuclear complexes. I Selective formation and crystal structure of (+)6C0D0-bis(tris(L-cysteinato-N,S)cobaltate(III)-.MU.-S,.MU.-S',.MU.-S")cobalt(III) nitrate pentahydrate.

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The crystal structure and the absolute configuration of the selectively formed title isomer, (+)600CD-[Co{Co(L-cys-N,S)3}2](NO3)2·5H2O, have been determined by X-ray diffraction. In the (+)600CD isomer, the six L-cysteinates coordinate through the nitrogen and sulfur atoms to give two terminal [Co(L-cys-N,S)3] moieties. The central cobalt atom spans the six sulfur atoms in these terminals to form a trinuclear structure. The (+)600CD isomer takes selectively a ΛLLLΛLLL configuration, in which both of the two terminals have a ΛLLL-fac(S) configuration, and the six sulfur donor atoms take an R one. The L-cysteinate chelate rings take a lel conformation along the C3 axis and the carboxyl or carboxylato groups take the axial orientations forming the intramolecular hydrogen bonds. The (−)600CD isomer is assigned to the ΔLLLΔLLL configuration on the basis of the electronic absorption, CD, and 13C NMR spectral behaviors. The selective formation for each of the (+)600CD and (−)600CD isomers is discussed in relation to their reaction conditions.
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