Abnormal solvent effects on hydrogen atom abstraction. 3. Novel kinetics in sequential proton loss electron transfer chemistry

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DOIResolve DOI: http://doi.org/10.1021/jo051474p
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TypeArticle
Journal titleJournal of Organic Chemistry
ISSN0022-3263
Volume70
Issue22
Pages89828990; # of pages: 9
SubjectAcetone; Electron transitions; Hydrogen; Ionization; Organic solvents; Rate constants; Reaction kinetics; Abnormal solvent effects; Benzonitrile; Electron transfer; Proton loss; Phenols; 1,1 diphenyl 2 picrylhydrazyl; 2,2' methylene bis(4 methyl 6 tert butylphenol); acetone; acetonitrile; benzonitrile; cyclohexanone; dimethyl sulfoxide; hydrogen; phenol derivative; solvent; unclassified drug; article; chemical reaction kinetics; chemical structure; electron transport; ionization; proton transport; reaction analysis
AbstractA 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 →rds SH+ + -OAr →dpph. 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. © 2005 American Chemical Society.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276451
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Record identifier21b8dc7b-d32d-4f84-a5fb-75743ca35d88
Record created2015-10-13
Record modified2016-05-09
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