Copper complexes as biomimetic models of catechol oxidase:
mechanistic studies
Koval, I.A.
Citation
Koval, I. A. (2006, February 2). Copper complexes as biomimetic models of catechol
oxidase: mechanistic studies. Retrieved from https://hdl.handle.net/1887/4295
Version: Corrected Publisher’s Version
License: Licence agreement concerning inclusion of doctoral thesis in theInstitutional Repository of the University of Leiden Downloaded from: https://hdl.handle.net/1887/4295
Copper complexes
as bi
omi
met
i
c models of cat
echol oxi
dase:
mechani
st
i
c st
udi
es
PROEFSCHRIFT
ter verkrijging van
de graad van Doctor aan de Universiteit Leiden op gezag van de Rector M agnificus Dr. D. D. Breimer,
hoogleraar in de faculteit der W iskunde en Natuurwetenschappen en die der Geneeskunde, volgens besluit van het College voor Promoties
te verdedigen op donderdag 2 februari 2006 klokke 16:15 uur
door
Iryna A. Koval
Samenstelling promotiecomissie
Promotor: Prof. Dr. J. Reedijk Co-promotor: Dr. P. Gamez
Referent: Dr. C. Belle (Université J. Fourier, Grenoble, Frankrijk) Overige Leden: Prof. Dr. J. Brouwer
Prof. Dr. B. Krebs (W estfälische W ilhelms-Universität M ünster, Duitsland)
Dr. E. Bouwman
“A scientist in his laboratory is not a mere technician: he is also a child confronting natural phenomena that impress him as though they were fairy tales.” Marie Sklodowska Curie
Table of Contents
Chapter 1. Introduction… … … ..7 Chapter 2. Synthetic route to novelasymmetric dinucleating ligands.
Crystalstructure and properties of the complex
[Cu2(py3asym)(H2O)1.5(NO3)2.5](NO3)0.5… … … ...51
Chapter 3. Structuraldiversity in CuII,CoIIand M nIIcomplexes of a phenol-based ligand containing amine,pyridine and formylfunctions:3D structures and solution
studies… … … .… 63 Chapter 4. Dinuclear CuIIcomplexes with the new phenol-based ligand
bearing pyridine and thiophene substituents:synthesis, characterization and interaction with catechol
substrates… … … ....89 Chapter 5. X-ray 3D structures and properties of two copper(II)
complexes with the asymmetric phenol-based N,O,S-ligand. Influence of the counter ion on the crystalpacking… … … .… .109 Chapter 6. Proton NM R spectroscopy and magnetic properties
of a solution-stable dicopper(II) complex bearing
a single ȝ-hydroxo bridge… … … ..… 125 Chapter 7. Catecholase activity of a ȝ-hydroxodicopper(II)
macrocyclic complex:structures,intermediates
Chapter 8. Catecholase activity of a copper(II) complex with the macrocyclic ligand [22]pr4pz:
unraveling catalytic mechanisms.………..………169
Chapter 9. Summary, general discussion and outlook.………...195
Samenvatting (Summary in Dutch).……….…………...207
Ʉɨɪɨɬɤɢɣ ɡɦɿɫɬ (Summary in Ukrainian).………..…………...211
Curriculum Vitae.……….……….218
List of publications.……….………..220
