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CHEMISTRY OF SINGLET OXYGEN—XXVIII *. STERIC AND ELECTRONIC EFFECTS ON THE REACTIVITY OF SULFIDES WITH SINGLET OXYGEN
Author(s) -
Kacher Mark L.,
Foote Christopher S.
Publication year - 1979
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/j.1751-1097.1979.tb07763.x
Subject(s) - chemistry , singlet oxygen , steric effects , sulfide , oxygen , alkyl , nucleophile , reactivity (psychology) , sulfur , photochemistry , singlet state , medicinal chemistry , aryl , electronic effect , organic chemistry , catalysis , excited state , medicine , physics , alternative medicine , pathology , nuclear physics
—The rates of reaction of singlet oxygen with a number of alkyl and aryl sulfides have been determined in CH 3 OH. The rate for diethylsulfide is 1.71 ± 0.06 × 10 7 M ‐1 s ‐1 . The addition of methyl groups α to the sulfur causes an approximate tenfold decrease in rate for each symmetrical pair. A similar effect is caused by replacement of alkyl by phenyl groups. The rates of substituted thioanisoles correlate well with σ(ρ= ‐1.6). but poorly with E P/2 (half‐peak oxidation potentials). A mechanism involving nucleophilic reaction of the sulfide with oxygen, rather than charge transfer is suggested.