Preparation, Stereochemistry, and CD Spectra of Cobalt(III) Complexes with 1,3-Propanedithiolate and 1,3-Propanedisulfinate. Crystal Structure and Absolute Configuration of (−)460CD-(1,3-Propanedisulfinato)(3,6-diazaoctane-1,8-diamine)cobalt(III) Perchlorate Monohydrate

The cis-α isomers of the 3,6-diazaoctane-1,8-diamine (trien) cobalt(III) complexes with 1,3-propanedithiolate (pdt) and 1,3-propanedisulfinate (pdsi) were selectively prepared and optically resolved. Of these isomers, the crystal structure and the absolute configuration of (−)460CD-[Co(pdsi)(trien)]ClO4·H2O have been determined by X-ray diffraction method. The complex cation takes a Δ-cis-α configuration. The 1,3-propanedisulfinate coordinates to cobalt atom through two sulfur atoms and its chelate ring takes a skew boat form with the λ conformation. The CD spectral behaviors in the d–d transition and the sulfur-to-metal (Co(σ*)←S(σ)) charge-transfer band regions are discussed in relation to the absolute configurations of the cobalt(III) complexes with sulfinate type sulfur donor atoms and the corresponding thiolate ones.