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Oxidation—reduction reaction of photoinduced benzyl radicals in water: para substituent effect

1993; Elsevier BV; Volume: 73; Issue: 3 Linguagem: Inglês

10.1016/1010-6030(93)90006-7

1873-2666

Ahmed M. Mayouff, Helge Lemmetyinen,

CO2 Reduction Techniques and Catalysts

Abstract The formation rate constant k 1 , the dissociation rate constant k 2 and the redox reaction rate constant k H 2 O of [X-C 6 H 4 -CH 2 -Cu 2+ ] intermediates (XCH 3 O, CH 3 , H, Cl) have been determined at room temperature in an aqueous solution of [(NH 3 ) 5 (XC 6 H 4 CH 2 -COO − )(Co 3+ )](ClO 4 ) 2 and Cu(ClO 4 ) 2 by time-resolved laser flash photolysis. The rate constant k 1 correlates well with the Hammett substituent parameter σ p . The reaction constant ϱ was —(1.415±0.111), indicating a high resonance effect.