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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 23, Number 6
BKCSDE 23(6)
June 20, 2002 

N,N'-Dimethylethylenediamine-N,N'-di-α-butyric Acid cobalt(Ⅲ)Complexes Utilizing Oxidation of Sulfur of S-Methyl-L-cysteine
Hyun-Jin Kim, Kyoung-Tae Youm, Jung Sung Yang, Moo-Jin Jun
Cobalt(3) complex, Ligand oxidation.
The Reaction of S-methyl-S-cystein (L-Smc) with racemic s-cis-[Co(dmedba)Cl2]-1 (H2dmedba=N,N'-dimethylenthylethylenediamine-N,N'-di-α-butyric acid) yields △-s-cis-[Co(dmedba)(L-Smc)] 2 with N,O-chelation. Oxidation of sulfur of 2 with H2O2 in a 1 : 1 mole ratio gives △-s-cis-[Co(dmedba)(L-S(O)mc)] 3 having an uncoordinated sulfenate group. Oxidation of sulfur of L-Smc with H2O2 in a 1 : 1 mole ratio produces S-methyl-L-cysteinsulfenate (L-S(O)mc) 5. Direct reaction of 1 with 5 in basic medium gives an N,O-chelated △-s-cis-[Co(dmedba)(S-S(O)mc)-N,O], which turned out to be same as obtained by oxidation of 2, while an N,S-chelated △-s-cis-[Co(dmedba)(L-Smc)-N,S] complex 4 is obtained in acidic medium from the reaction of 1 with 5. This is one of the rare [Co(N2O2-type ligand)9amino acid)] type complex preparations, where the reaction conditions determine which mode of N,O and N,S chelation modes is favored.
851 - 855
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