From mononuclear iron phthalocyanines in catalysis to μ-nitrido diiron complexes and beyond

• Published in: Catalysis today 2021-08, Vol.373, p.38-58
• Main Author: Sorokin, Alexander B.
• Format: Article
• Language: English
• Subjects: Binuclear complexes; Bio-inspired; Catalysis; Chemical Sciences; Environment and Society; Environmental Sciences; Oxidation; Phthalocyanine; μ-nitrido
• ISSN: 0920-5861; 1873-4308
• DOI: 10.1016/j.cattod.2021.03.016

[Display omitted] •Metal phthalocyanine complexes are the catalysts for oxidation and other reactions.•μ-Nitrido diiron complexes feature a particular structure and catalytic properties.•Mild oxidation of methane.•Oxidative defluorination of heavily fluorinated aromatic compounds.•Flexibility of binuclear macrocyclic platform. For a long time biomimetic oxidation catalysis was mainly associated with metal porphyrin complexes. Phthalocyanine complexes, also belonging to large family of macrocyclic complexes have been under-investigated as catalysts until recently. In this review, we present the development of phthalocyanine catalytic chemistry at IRCELYON with a topical focus on contributions from our group during last 20 years and discuss recent research directions from personal perspective. Catalytic chemistry of phthalocyanine complexes is a rapidly growing field including not only oxidations but also many other reactions. Recent discovery of remarkable catalytic properties of μ-nitrido diiron phthalocyanines will give a new impetus and should even accelerate this development. These binuclear N-bridged complexes emerge as promising bio-inspired catalysts, in particular, for challenging reactions such as a low temperature oxidation of methane and oxidative defluorination of heavily fluorinated aromatic compounds. The scope of their catalytic applications is constantly increasing. The bimetallic construction is flexible and has a significant potential for further development including implementation of different ligands, metals and bridging groups. Consequently, the properties of this scaffold can be fine-tuned by platform architecture thus providing novel tools for catalysis.