Reaction of ·CH2C(CH3)2OH Radicals with Cobalt(II) Tetrasulfophthalocyanine in Aqueous Solutions. A Pulse Radiolytic Study

Yacov Sorek, Haim Cohen, William A. Mulac, Klaus H. Schmidt, Dan Meyerstein

Research output: Contribution to journalArticlepeer-review

28 Scopus citations

Abstract

The reaction of cobalt(II) tetrasulfophthalocyanine, [CoII(tspc)]4-, with ·CH2C(CH3)2OH free radicals was studied. The results indicate that the first product formed is [(tspc)CoIIICH2C(CH3)2OH]4-. This product loses water via β elimination to yield [(tspc)CoIII,CH=C(CH3)2]4-. The decomposition of the latter compound yields [CoICtspc)]5- + OCHCH(CH3)2 at pH 9.5, [CoIII(tspc)]3- + CH2=C(CH3)2 at pH ~6, and mainly [CoII(tspc)]4- plus equal amounts of CH2=C(CH3)2 and OCHCH(CH3)2 at pH ~3. The results suggest that a pK of the water molecule trans to the aliphatic residue affects the mechanism of hydrolysis. A further reaction is observed, the exact nature of which is not fully understood. For comparison purposes the oxidation of [CoII(tspc)]4- by [formula-omitted] and its reduction by [formula-omitted]. were studied.

Original languageEnglish
Pages (from-to)3040-3046
Number of pages7
JournalInorganic Chemistry
Volume22
Issue number21
DOIs
StatePublished - 1 Jan 1983
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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