Mechanistic study of β-hydroxy elimination from [tetra sulphophthalocyanine CoIII-CR1R2CR3R4OH] in aqueous solutions. A pulse radiolysis study
Abstract
The reactions of cobalt(II) tetrasulphophthalocyanine, [CoII(tspc)]4– with ˙CH3, ˙CH2CH2OH, ˙CH(CH3)CH2OH, ˙CH(CH3)CH(CH3)OH and ˙CH2C(CH3)2OH free radicals have been studied. The results indicate that the first product formed in these reactions has the form [CoII—(tspc—R)]4–, where R is the aliphatic free radical, the exact nature of the bonding of ˙R to tspc is not clear. The complex [CoII—(tspc—R)]4– rearranges into [(tspc)CoIII—R]4– in a process obeying a first-order rate law. [(tspc)CoIII—CH3]4– decomposes into [CoIII(tspc)]3–+ CH4, whereas the complexes [(tspc)CoIII—CR1R2CR3R4OH]4– decompose into [CoIII(tspc)]3–+ R1R2CCR3R4+ OH–.