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KMID : 1059519960400070501
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Journal of the Korean Chemical Society
1996 Volume.40 No. 7 p.501 ~ p.508
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The Base-Catalysed Carbonato or Oxalato Ring Opening of cis-β-[Co(3,2,3-tet)(CO3 or C2O4)]+(3,2,3-tet=4,7-diazadecane-1,10-diamine)
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Yoon Doo-Cheon
Oh Chang-Eon
Kim Bok-Jo
Doh Myung-Ki
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Abstract
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The base-catalysed carbonato or oxalato ring opening of cis-β-[Co(3,2,3-tet)(CO3 or C2O4)]+(3,2,3-tet=4,7-diazadecane-1,10-diamine, C2O4=oxalate) has been investigated in aqueous solution and in mixed aqueous-organic solvent. The rearrangement of 3,2,3-tet and carbonato or oxalato ring opening of cis-β-[Co(3,2,3-tet)(CO3 or C2O4)]+ occurred via the dissociation of one of the two coordinating carbonato or oxalato oxygen atoms. The resulting product was cis-α-[Co(3,2,3-tet)(OH)(OCO2 or OC2O3)3]. It has been suggested that the base-catalysed reaction of cis-β-[Co(3,2,3-tet)(CO3 or C2O4)]+ takes place via the Dcb(dissociative conjugated base) mechanism. The other oxygen atom of carbonato or oxalato was dissociated continuously to give cis-α-[Co(3,2,3-tet)(OH)2]+. Cis-α-[Co(3,2,3-tet)(OH)2]+ was isomerized to cis-β-[Co(3,2,3-tet)(OH)2]+.
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