title: Electronic ménages a trois: a molecular orbital perspective of protonated ferryl intermediates and synthetic models.
abstract: Presented here is a molecular orbital perspective of various S=1 iron(IV)-hydroxo compound II intermediates as well as of synthetic heme and nonheme analogues. A key conceptual issue concerns how the iron(IV) center in these species coexists with highly reducing alkoxide, thiolate, phenolate, and hydroperoxide ligands. We suggest that a clue to this conundrum involves a three-way splitting of the spin density among the iron and two pi-basic ligands, which effectively delocalizes the high positive charge away from the iron.
authors.affiliation: Department of Chemistry, University of Tromsø, Breivika, N-9037 Tromsø, Norway.
authors.forename: Jeanet
authors.initials: J
authors.lastname: Conradie
authors.forename: Ingar
authors.initials: I
authors.lastname: Wasbotten
authors.forename: Abhik
authors.initials: A
authors.lastname: Ghosh
mesh_terms: D006420:Hemeproteins / Q000737:chemistry; D007501:Iron / Q000737:chemistry* / Q000378:metabolism; D008024:Ligands; D008956:Models, Chemical; D008958:Models, Molecular; D019159:Nonheme Iron Proteins / Q000737:chemistry; D011522:Protons
chemical_list: D006420:Hemeproteins; D008024:Ligands; D019159:Nonheme Iron Proteins; D011522:Protons; C066317:ferryl iron; D007501:Iron