Abstract
Abstract Mechanism and kinetics of hydrogen atom transfer reaction from mesitylene (M) to triplet chloranil (3CA) in 1,2-dichloroethane (DCE) at room temperature have been studied by means of picosecond (ps) and nanosecond (ns) laser flash photolysis techniques. It was found that the hydrogen transfer resulting in the formation of chloranil semiquinone radical (CAH·) proceeded through a partial charge-transfer (CT) triplet complex between 3CA and M as an intermediate. No ion-pair formation was observed. The triplet complex showed transient absorption bands in the visible and near infrared regions. The association constant (KT=28 dm3 mol−1) and lifetime (τC=32 ns) of the complex were estimated from a kinetic analysis for 3CA quenching. From these results, combined with those of the quantum yield of CAH· formation, the first order rate constants for the hydrogen transfer and intersystem crossing in the triplet complex were estimated to be (1.7 and 1.4)×107 s−1, respectively.
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