Single-atom bridged diiron macrocyclic complexes: influence of the structure on catalytic properties.
Résumé
Metal phthalocyanine and porphyrin complexes are widely used in many catalytic applications and their catalytic chemistry is well-documented. These macrocycles can be assembled in more elaborated structures, e.g. µ-oxo, µ-nitrido and µ-carbido diiron complexes which haven’t been considered as catalysts until recently. Quite unexpectedly, some single-atom bridged diiron complexes are capable of reacting with oxidants retaining their dimeric structure to form ultra high-valent diiron species.These short-living species were detected and characterized by UV-vis, EPR, ESI-MS, Fe K edge EXAFS, XANES and Mössbauer techniques.
Of particular interest are the unusual catalytic properties of these highly electrophilic species which are able to oxidize methane and to perform oxidative transformation of the aromatic C-F bonds under very mild conditions. Mechanistic issues of this unusual reactivity and influence of the structure on the catalytic properties are discussed.