Mechanistic studies of the sensitized photoreduction of bis(acetylacetonato)copper(II) by phenylalkyl ketones |
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| Institution: | 1. Instituto de Investigaciones de Fisicoquímica de Córdoba (INFIQC — CONICET), Departamento de Matemática y Física, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, X5000HUA Córdoba, Argentina;2. Instituto de Investigaciones de Fisicoquímica de Córdoba (INFIQC — CONICET), Departamento de Fisicoquímica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, X5000HUA Córdoba, Argentina |
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| Abstract: | Bis(acetylacetonato)copper(II) (Cu(acac)2) interacts with both the triplet excited state and the triplet biradical of phenylalkyl ketones which undergo the Norrish type II reaction. Mechanistic studies by static quenching methods show that the triplet biradicals interact with the paramagnetic copper species, leading to the preferential formation of cyclobutanols without the formation of new products; in the presence of Ph3P the former interaction causes the known reduction of Cu(acac)2) to Cu(acac)(Ph3P)2, with a rate constant of about 6 × 109 M−1 s−1. It is shown that Ph3P interacts with one reactive intermediate, the triplet excited state ketone. The results of extensive kinetic analysis strongly support the proposed reaction mechanism. |
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