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Abnormal Solvent Effects on Hydrogen Atom Abstraction. 3. Novel Kinetics in Sequential Proton Loss Electron Transfer Chemistry

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journal contribution
posted on 28.10.2005, 00:00 by Grzegorz Litwinienko, K. U. Ingold
A prolonged search involving several dozen phenols, each in numerous solvents, for an ArOH/2,2-diphenyl-1-picrylhydrazyl (dpph) reaction that is first-order in ArOH but zero-order in dpph has reached a successful conclusion. These unusual kinetics are followed by 2,2‘-methylene-bis(4-methyl-6-tert-butylphenol), BIS, in five solvents (acetonitrile, benzonitrile, acetone, cyclohexanone, and DMSO). In 15 other solvents the reactions were first-order in both BIS and dpph (i.e., the reactions followed “normal” kinetics). The zero-order kinetics indicate that in the five named solvents the BIS/dpph reaction occurs by sequential proton loss electron transfer (SPLET). This mechanism is not uncommon for ArOH/dpph reactions in solvents that support ionization, and normal kinetics have always been observed previously (see Litwinienko, G.; Ingold, K. U. J. Org. Chem. 2003, 68, 3433 and Litwinienko, G.; Ingold, K. U. J. Org. Chem. 2004, 69, 5888). The zero-order kinetics found for the BIS/dpph reaction in five solvents, S, imply that BIS ionization has become the rate-determining step (rds, rate constants 0.20−3.3 s-1) in the SPLET reaction sequence:  S + HOAr ⇌ S− HOAr SH+ + -OAr SH+ + OAr + dpph- → S + OAr + dpph-H, where ArOH = BIS. Some properties specific to BIS that may be relevant to its relatively slow ionization in the five solvents are considered.