title: High-valent transition metal centers and noninnocent ligands in metalloporphyrins and related molecules: a broad overview based on quantum chemical calculations.
abstract: Using density functional theory, we have carried out a quantum chemical survey of high-valent transition metal porphyrins and related compounds. Discussed herein are recent developments on metalloporphyrin pi-cation radicals, high-valent manganese and iron porphyrins and heme protein intermediates, nickel(III) porphyrinoids, coenzyme F430, and high-valent transition metal corroles. In particular, we focus on whether the molecules of interest feature "true" high-valent metal centers, whether the ligands are oxidized instead, i.e. are noninnocent, or whether the electronic structures fall somewhere along the continuum between these scenarios.
authors.affiliation: Institute of Chemistry, Faculty of Science, University of Tromsø, Norway. abhik@chem.uit.no
authors.forename: A
authors.initials: A
authors.lastname: Ghosh
authors.forename: E
authors.initials: E
authors.lastname: Steene
mesh_terms: D002412:Cations; D003300:Copper / Q000737:chemistry / Q000378:metabolism; D007501:Iron / Q000737:chemistry / Q000378:metabolism; D008024:Ligands; D008345:Manganese / Q000737:chemistry / Q000378:metabolism; D008665:Metalloporphyrins / Q000737:chemistry* / Q000378:metabolism; D008956:Models, Chemical; D009532:Nickel / Q000737:chemistry / Q000378:metabolism; D009195:Peroxidase / Q000737:chemistry / Q000378:metabolism; D011166:Porphyrins / Q000737:chemistry / Q000378:metabolism; D011789:Quantum Theory
chemical_list: D002412:Cations; D008024:Ligands; D008665:Metalloporphyrins; D011166:Porphyrins; C431863:corrole; D008345:Manganese; C023540:factor F430; D003300:Copper; D009532:Nickel; D007501:Iron; D009195:Peroxidase