Skip to Main content Skip to Navigation
Theses

Transfert couplé d'électron et de proton dans des complexes de métaux de transition modèles et d'intérêts biomimétiques. Etudes mécanistiques par une approche électrochimique.

Abstract : The biomimetic complexes efficiency involving Proton Coupled electron Transfer could be inherent to the concertation of the both transfers, avoiding the highly energetic intermediates. We have determined the parameters influencing a concerted mechanism thanks to an experimental electrochemical study of an osmium complex ([OsII(bpy)2py(H2O)](PF6)2). We have identified the PCET mechanism for each osmium complex electrochemical couples: the OsII(H2O)/OsIII(OH) follows a stepwise mechanism whereas the OsIII(OH)/OsII=O presents a concerted mechanism. By comparison of these systems, we have been able to determine the parameters promoting a concerted mechanism useful to elaborate an ideal complex: it should present a rigid coordination sphere in order to have a high standard rate constant, a large acidity constant gap, a proximal proton acceptor, a selected environment to avoid an association with an anion instead of the proton acceptor and an adapted ligands in agreement with solubility and stability criteria. Then, a SOD biomimetic manganese complex study has allowed to apply the osmium complex study methodology and to confirm that the proton acceptor concentration increase can cause the prevalence of the concerted mechanism.
Document type :
Theses
Complete list of metadatas

Cited literature [136 references]  Display  Hide  Download

https://tel.archives-ouvertes.fr/tel-00424935
Contributor : Anne-Lucie Teillout <>
Submitted on : Monday, October 19, 2009 - 1:44:08 PM
Last modification on : Wednesday, October 21, 2020 - 9:40:04 AM
Long-term archiving on: : Wednesday, June 16, 2010 - 12:53:17 AM

Identifiers

  • HAL Id : tel-00424935, version 1

Citation

Anne-Lucie Teillout. Transfert couplé d'électron et de proton dans des complexes de métaux de transition modèles et d'intérêts biomimétiques. Etudes mécanistiques par une approche électrochimique.. Autre. Université Paris-Diderot - Paris VII, 2009. Français. ⟨tel-00424935⟩

Share

Metrics

Record views

413

Files downloads

3526