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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Managanese and dicopper complexes for bioinspired oxidation reactions: catalytic and mechanistic studies on C-H and C=C oxidations

Garcia Bosch, Isaac 20 December 2011 (has links)
Enzymes are high-weight molecules which catalyze most of the metabolic processes in living organisms. Very often, these proteins contain one or more 1st row transition metal ions in their active center (Fe, Cu, Co, Mn, Zn, etc.), and are known as metalloenzymes or metalloproteins. Among these, metalloenzymes that activate molecular oxygen and use it as terminal oxidant stand out because of the wide range of catalyzed reactions and their exquisite selectivity. In this PhD dissertation we develop low-weight synthetic bioinspired complexes that can mimic structural and/or functional features of the active center of oxigenases. In the first part, we describe the use of unsymmetric dinuclear Cu complexes which are capable of performing the oxidation of phenols and phenolates in a analogous manner of the tyrosinase protein. In the second part, we describe the use of mononuclear manganese complexes in the oxidation of alcanes and alquenes. / Els enzims són molècules d’elevat pes molecular que catalitzen la majoria de processos metabòlics en els éssers vius. Sovint aquestes proteïnes contenen un o diversos ions metàl•lics de la 1a sèrie de transició en el seu centre actiu (Fe, Cu, Co, Mn, Zn, etc.), essent anomenats metal•loenzims o metal•loproteïnes. D’aquests, els metal•loenzims que activen la molècula d’oxigen i l’utilitzen com a oxidant ressalten per la varietat de reaccions catalitzades i la seva exquisida selectivitat. En aquesta tesi doctoral, desenvolupem complexos de baix pes molecular que puguin mimetitzar estructural i/o funcionalment els centres actius de les oxigenases. En una primera part, es descriu la utilització de complexos assimètrics dinuclears de Cu capaços de dur a terme l'oxidació de fenols i fenolats de manera similar a la proteïna tirosinasa. En una segona part, es descriu l'ús de complexos mononuclears de manganès per a l'oxidació d'alcans i alquens.

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