Preparation and some properties of cobalt(III) complexes with D-penicillaminate and its derivatives.

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Three kinds of [Co(terdentate-N,O,S)2] type complexes were newly prepared; here terdentate-N,O,S denotes D-penicillaminate (D-pen), S-methyl-D-penicillaminate (D-smp) and S-methyl-L-cysteinate (L-smc). Each of the D-smp and L-smc complexes was chromatographically separated into three possible isomers; the D-pen complex was separated into two isomers. These isomers were characterized from their electronic absorption, CD and 1H NMR spectra. Two isomers isolated for [Co(D-pen)2]− were assigned to trans(N) and trans(O), respectively, on the basis of the spectral behavior of the sulfur-to-metal charge transfer band and the reaction with dimethyl sulfate. Three isomers for [Co(D-smp)2]+ were derived from each of two isomers for [Co(D-pen)2]+ by the reaction with dimethyl sulfate. The electronic absorption and CD spectral behaviors are discussed in relation to the comparison of the thioether and thiolato type complexes.
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