Novel N-bridged diiron phthalocyanine complexes : synthesis, characterization and application in oxidation
type: Distribution
access URL: https://theses.hal.science/tel-00881309
format: HTML
issued: 2026-05-09T02:38:57.525556
modified: 2026-05-09T02:38:57.499874

test_moissonnage_selune
type: Agent

Novel N-bridged diiron phthalocyanine complexes : synthesis, characterization and application in oxidation
type: Dataset
contact point: Organization
  fn: CCSD
keyword: complexe-du-fer
keyword: oxydation-bio-inspiree
keyword: -nitrido-dimere
keyword: theses
keyword: iron-complex
keyword: chimothechemical-sciencesother
keyword: infoeu-reposemanticsdoctoralthesis
keyword: oxidation
keyword: catalysis
keyword: catalyse
keyword: oxydation
keyword: phthalocyanine
keyword: -nitrido-dimer
keyword: bioinspired-oxidation
keyword: xylene
keyword: toluene
landing page: https://theses.hal.science/tel-00881309
description: The synthetic approach was developed for the preparation of N-bridged diiron phthalocyanines substituted by different electron-withdrawing alkylsulfonyl substituents. Six novel phthalocyanines bearing small (methylsulfonyl, ethylsulfonyl and hexylsulfonyl) and bulky (t-butylsulfonyl, adamantylsulfonyl and cyclohexylsulfonyl) substituents have been prepared and characterized by electrospray ionization mass spectrometry (ESI-MS), UV-Vis, FT-IR and EPR. Two complexes (with hexylsulfonyl and t-butylsulfonyl substituents) were characterized in addition by Mössbauer techniques, X-ray photoelectron spectroscopy (XPS) and Fe K-edge X-ray absorption spectroscopy (XANES, EXAFS, high resolution Kβ emission spectroscopy). It has been evidenced that the electronic state of iron in these complexes depends on the size of the substituents. While N-bridged diiron phthalocyanines having methylsulfonyl, ethylsulfonyl and hexylsulfonyl substituents are cationic (PcFeIVNFeIVPc)+N3- complexes, N-bridged diiron phthalocyanines with bulkier t-butylsulfonyl, adamantylsulfonyl and cyclohexylsulfonyl substituents are formally neutral PcFeIIINFeIVPc species. The catalytic properties of six N-bridged diiron phthalocyanines have been studied, using tert-butyl hydroperoxide (tBuOOH) as the oxidant in the oxidation of toluene, p-xylene as well as in the oxidation of various alcohols. This thesis demonstrates the efficiency of N-bridged diiron phthalocyanines substituted by electron-withdrawing alkylsulfonyl groups as oxidation catalysts, in conditions required by environmental and industrial preoccupations
identifier: NNT: 2010LYO10016
issued: 2026-05-09T02:38:57.519220
language: en
modified: 2026-05-09T02:38:57.519224