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Laser‐flash photolysis of naphthyl diselenides; reactivities of naphthylseleno radicals
Author(s) -
Alam Maksudul M.,
Ito Osamu,
Koga Yoshinori,
Ouchi Akihiko
Publication year - 1998
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(1998)30:3<193::aid-kin4>3.0.co;2-n
Subject(s) - flash photolysis , chemistry , radical , photochemistry , reactivity (psychology) , reaction rate constant , photodissociation , organic chemistry , kinetics , medicine , alternative medicine , physics , pathology , quantum mechanics
Transient absorption spectra of 1‐naphthylseleno (1‐NaphSe˙), and 2‐naphthylseleno (2‐NaphSe˙) radicals, which are generated by laser‐flash photolysis of the corresponding diselenides, were observed. The reactions of 1‐NaphSe˙, and 2‐NaphSe˙ with 2‐methyl‐1,3‐butadiene and α‐methylstyrene were investigated by following the decay rates of these seleno radicals. By both steady‐state and laser‐flash photolysis, it is proved that these seleno radicals add to alkenes in a reversible manner. The reaction rate constants for such reversible addition reactions were determined by conducting the reaction in the presence of O 2 , which traps selectively the carbon‐centered radicals formed by the addition reaction of the seleno radicals to the alkenes. The reactivity of 2‐NaphSe˙ is higher than that of 1‐NaphSe˙, both of which are less reactive than PhSe˙. These reactivities were interpreted with the properties of SOMO calculated by MO method. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 193–200, 1998.