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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 45, Number 3
JKCSEZ 45(3)
June 20, 2001 
 
Title
 Studies on the Oxygen-Atom-Transfer Reactions of Peroxo Vanadium(V) Complexes

Peroxo Vanadium(V) 화합물들에 의한 산소 원자 전이 반응에 관한 연구
Author
 Tae-Jin Won

원태진
Keywords
Abstract
 Peroxo-vanadium(V) 화합물인 VO(O2)2(pic)2-와 VO(O2)(nta)2- 그리고 VO(O2)(dipic)-는 pH4.0의 수용액 안에서 thiolato-cobalt(Ⅲ)화합물인 (en)2Co(SCH2CH2NH2)2+와 산소 원자 전이 반응을 일으킨다. 이들의 산소 원자 전이 반응에서 각각(35±1)와 (4.8±0.4)×10-2 그리고 (8.6±0.5)×10-4의 속도상수(M-1S-1)을 얻었다. VO(O2)2(pic)2-에 배위되어 있는 peroxide는 산소 원자 전이 반응에서 활성화되어지나 VO(O2)(nta)2- 와 VO(O2)(dipic)-에 배위되어 있는 peroxide는 불활성화된다. 우리는 이 논문에서 peroxo vanadium(V) 화합물의 산소 원자 전이의 반응 경로는 친전자성의 peroxide 리간드가 친핵성의 substrate와 직접적인 반응에 의하여 이루어진다고 제안하였다.

The reaction of peroxo vanadium(V) complexes, VO(O2)2(pic)2-, VO(O2)(nta)2-, and VO(O2)(dipic)- with thiolato-cobalt(III), (en)2Co(SCH2CH2NH2)2+resulted in an oxygen-atom transfer in aqueous solutions. Rate constants (M-1S-1) for these reactions were (35±1), (4.8±0.4)×10-2 , and (8.6±0.5)×10-4 , respectively. The coordinate peroxide was activated in the oxygen-atom-transfer reaction of VO(O2)2(pic)2-, but it is not the case for VO(O2)(nta)2- and VO(O2)(dipic)-. In this paper, we proposed that the direct attack of an electrophilic peroxide to a nucleophilic substrate occurs in the oxygen-atom transfer pathway of peroxo vanadium(V) complexes.
Page
 213 - 218
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