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Reactivity difference between protolytic forms of some macrocyclic chromium(III) complexes in ligand substitution and electron transfer processes

Mills, Andrew and Katafias, Anna and Chatłas, Janusz and Impert, Olga and Kita, Przemysław and Madej, Edyta and Topolskia, Adrian and Wrzeszcz, Grzegorz (2010) Reactivity difference between protolytic forms of some macrocyclic chromium(III) complexes in ligand substitution and electron transfer processes. Inorganica Chimica Acta, 363 (11). pp. 2346-2356. ISSN 0020-1693

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Abstract

The review provides insight into the mechanism of ligand substitution and electron transfer (from chromium( III) to iron(III)) by comparison of the reactivity of some tetraazamacrocyclic chromium(III) complexes in the conjugate acid-base forms. Use of two geometrical isomers made possible to estimate the influence of geometry and protolytic reactions in trans and cis position towards the leaving group on the rate enhancement. Studies on the reaction rates in different media demonstrated the role played by outer sphere interactions in a monodentate ligand substitution.