Bioinspired catalysts for phosphoryl transfer reactions [Elektronische Ressource] / vorgelegt von Malgorzata Jagoda

Bioinspired Catalysts for Phosphoryl Transfer Reactions Inaugural-Dissertation zur Erlangung der Doktorwürde der Naturwissenschaftlich-Mathematischen Gesamtfakultät der Ruprecht-Karls-Universität Heidelberg Vorgelegt von Diplom-Chemikerin Malgorzata Jagoda aus Tarnow, Polen 2005 Short summary in English Phosphoryl transfer reactions are ubiquitous in biology and are usually catalyzed by metalloenzymes. For a number of phosphoryltransfer enzymes, including the exonuclease subunit of DNA polymerase I, a mechanism involving two metal ions and double Lewis-acid activation of the substrate, combined with leaving group stabilisation, has been proposed. Aim of this thesis was the study of low-molecular-weight models of phosphoryl transfer metalloenzymes. The focus was in particular on the macrocyclic dicopper(II) complex LCu , 2which is the first transesterification catalyst for highly inert dialkyl phosphates and a mimic of the exonuclease subunit of DNA polymerase I. For the first time, a crystal structure of LCu with a coordinated phosphodiester was 2obtained. [LCu (1,3-µ-DMP)(NO )](NO ) (2) contains a 1,3- bridging phosphodiester. 2 3 3 2By extensive UV-Vis and pH metric titrations, the metal complex species present in methanolic LCu /DMP solution have been identified.