Abstract
Reactions of cobalt(II) sulphophthalocyanine dimers with the free radicals e–(aq), OH, ĊH2OH, Me2C(OH)ĊH2, and Me2ĊOH have been investigated by optical pulse-radiolysis methods. Rate constants have been determined to be ca. 3 × 109 dm3 mol–1 s–1 for OH and e–(aq), but an order of magnitude less for the alcohol radicals. Similarity has been observed in the spectra produced by OH and Me2C(OH)ĊH2 although the kinetics are markedly different. It is proposed that, following ligand-radical formation by OH, oxidation of the metal centre and subsequent dimer splitting occurs. In the case of Me2C(OH)ĊH2 the formation of a metal–alkyl bond appears likely, followed by splitting of the dimeric intermediate. The transient spectra produced by e–(aq), ĊH2OH, and Me2ĊOH are also very similar to one another. In these cases spectral behaviour suggests reduction of the metal centre by a ligand radical, followed by dimer dissociation (t½ca. 2 ms).
Sign-in/Register to access full text options 
Free) 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call
