Introduction High-valent iron( IV)–oxo species are key intermediates in biology and involved in essential oxidation processes in Nature. Subsequent kinetics studies showed that these oxidants are able to even oxidize methane to formic acid efficiently. However, the analysis of the iron( III)–hydroperoxo bond strength reveals major differences for the (Pc 1)FeN(Pc SO 2R)Fe IIIOOH system as compared to (Pc SO 2R)FeN(Pc 1)Fe IIIOOH system, and, hence binding of a terminal oxidant will be preferentially on more electron-rich sides. DFT calculations show that both isomers are close in energy. Analyses of fragmentation patterns indicated a preferential formation of hydroperoxo and oxo moieties at more electron-rich iron sites of both heteroleptic μ-nitrido complexes. Sufficient amounts of these transient species were trapped in the quadrupole region of the mass-spectrometer and underwent a CID-MS/MS fragmentation. When m-CPBA was used as the oxidant, the formation of diiron oxo species (Pc SO 2R)FeNFe(Pc 1) O was also evidenced. Cryospray ionization mass spectrometry (CSI-MS) characterized both hydroperoxo and diiron oxo species in the presence of H 2O 2.

A reaction with terminal oxidants gives two isomeric iron( IV)–oxo and iron( III)–hydroperoxo species with abundances dependent on the equatorial ligand. Heteroleptic μ-nitrido diiron phthalocyanine complexes having an unsubstituted phthalocyanine (Pc 1) and a phthalocyanine ligand substituted with electron-withdrawing alkylsulfonyl groups (Pc SO 2R) were prepared and characterized. We propose a novel intramolecular approach to determine the structural features that govern the catalytic activity of iron( IV)–oxo sites. In our aim to create better and more efficient oxidants of H-atom abstraction reactions, we have investigated a unique heteroleptic diiron phthalocyanine complex. Iron( IV)–oxo species have been identified as the active intermediates in key enzymatic processes, and their catalytic properties are strongly affected by the equatorial and axial ligands bound to the metal, but details of these effects are still unresolved. E-mail: d Centre Commun de Spectrométrie de Masse UMR 5246, CNRS-Université Claude Bernard Lyon 1, Université de Lyon, Bâtiment Curien, 43, bd du 11 Novembre, 69622 Villeurbanne Cedex, France e Synchrotron Soleil, L'orme des merisiers, St-Aubin, 91192 Gif-sur-Yvette, France Einstein, 69626 Villeurbanne Cedex, France. E-mail: c Institut de Recherches sur la Catalyse et l'Environnement de Lyon (IRCELYON), UMR 5256, CNRS-Université Lyon 1, 2, av. E-mail: b Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science, The University of Manchester, 131 Princess Street, Manchester M1 7DN, UK. * b a Gebze Technical University, Department of Chemistry, P.O. Sci., 2015, 6, 5063-5075 Site-selective formation of an iron( IV)–oxo species at the more electron-rich iron atom of heteroleptic μ-nitrido diiron phthalocyanines †

Geometry dash pc1.9