Effect of Electron Scavengers on the Chain Reaction of Sulfo-Group Substitution for Bromine in 1-Bromo-2-hydroxynaphthalene Photosensitized with Tris(2,2′-bipyridyl)ruthenium(II)

Author： Ivanov V. Lyashkevich S.

Publisher： MAIK Nauka/Interperiodica

ISSN： 0018-1439

Source： High Energy Chemistry, Vol.39, Iss.5, 2005-09, pp. : 304-308

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Abstract

The effect of electron scavengers (carbon tetrachloride, chloroform, and chloranil) on the chain radical-ion reaction of sulfo-group substitution for bromine in 1-bromo-2-hydroxynaphthalene photosensitized with a tris(2,2′-bipyridyl)ruthenium(II) complex was studied in an aqueous solution of sodium sulfite. It was found that “ sacrificial” electron scavengers enhanced the quantum yield of the photosensitized substitution reaction. Using the flash photolysis technique, it was shown that the electron scavengers reacted with the ruthenium(I) complex formed as a result of dissociation of a radical-ion pair in the initiation step. The rates constants for the reaction of chloroform, carbon tetrachloride, and chloranil with the ruthenium(I) complex are 1.5 × 10⁴, 1.2 × 10⁷, and 1.5 × 10⁹ dm³ mol⁻¹ s⁻¹, respectively. The chain length of the substitution reaction in aqueous solution in the presence of carbon tetrachloride is 220 ± 20.