The Synthesis and Oxidation of Mixed Cobalt(III) Complexes with Dimethyldithiocarbamato and Diamine Ligands, and the Crystal Structure of (+)500CD-Dimethyldithiocarbamatobis(ethylenediamine)cobalt(III) Bis[μ-(R,R)-tartrato]dianxtimonate(III) Pentahydrate

Abstract Dithiocarbamato complexes, [Co(dtc)3−n(diamine)n]n+ (n=1 and 2 and dtc=dimethyldithiocarbamate) were newly prepared and characterized by means of their absorption, CD, and MCD spectra. (+)500CD-[Co(dtc)(en)2][Sb2(R,R-C4H2O6)2]·5H2O crystallized in the monoclinic space group of P21 with a=14.630(3), b=9.300(1), c=12.023(5) Å, β=110.78(3)°, V=1529.4(8) Å3, and Z=2. The refinement of 3346 reflections (Mo Kα radiation) led to R=0.073. The dtc complex had a Λ configuration. The Co–N bond trans to the dtc sulfur atom was longer by 0.026 A than the cis one. A novel oxidation derivative, [Co{(dimethylamino)thioxomethanesulfinato-O,S}(en)2]2+, was prepared and characterized by means of its XPS spectrum.