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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 40, Number 7
JKCSEZ 40(7)
February 20, 1996 

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)

염기성 촉매에 의한 cis-β-[Co(3,2,3-tet)(CO3 or C2O4)]+(3,2,3-tet=4,7-diazadecane-1,10-diamine)에 대한 Carbonato 혹은 Oxalato 리간드의 고리열림 반응
Doo Cheon Yoon, Chang Eon Oh, Bok Jo Kim, Myung Ki Doh

염기성 용액속에서 cis-β-[Co(3,2,3-tet)(CO3 or C2O4)]+(3,2,3-tet=4,7-diazadecane-1,10-diamine, C2O4=oxalate)에 대한 carbonato 혹은 oxalato 리간드의 고리열림 반응이 수용액 및 유기용매-물 혼합용매속에서 조사되었다. 그 결과 cis-β-[Co(3,2,3-tet)(CO3 or C2O4)]+에서 킬레이트된 CO32- 혹은 C2O42-의 두 개의 산소원자 중 한 개가 해리하여 OH-가 치환되고 3,2,3-tet의 재배열이 일어나 cis-α-[Co(3,2,3-tet)(OH)(OCO2 or OC2O3)3]가 생성되었고, 반응은 해리성인 Dcb(dissociative conjugated base) 메카니즘으로 진행되었다. 연이어 C2O42- 혹은 CO32-의 나머지 한 개의 산소원자가 해리하여 cis-α-[Co(3,2,3-tet)(OH)2]+가 생성되었고 이것은 다시 cis-β-[Co(3,2,3-tet)(OH)2]+로 이성질화 반응이 일어났다.

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]+.

501 - 508
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