title: Secondary coordination sphere influence on the reactivity of nonheme iron(II) complexes: an experimental and DFT approach.
abstract: The new biomimetic ligands N4Py(2Ph) (1) and N4Py(2Ph,amide) (2) were synthesized and yield the iron(II) complexes [Fe(II)(N4Py(2Ph))(NCCH3)](BF4)2 (3) and [Fe(II)(N4Py(2Ph,amide))](BF4)2 (5). Controlled orientation of the Ph substituents in 3 leads to facile triplet spin reactivity for a putative Fe(IV)(O) intermediate, resulting in rapid arene hydroxylation. Addition of a peripheral amide substituent within hydrogen-bond distance of the iron first coordination sphere leads to stabilization of a high-spin Fe(III)OOR species which decays without arene hydroxylation. These results provide new insights regarding the impact of secondary coordination sphere effects at nonheme iron centers.
authors.affiliation: Department of Chemistry, The Johns Hopkins University, 3400 North Charles Street, Baltimore, Maryland 21218, USA.
authors.forename: Sumit
authors.initials: S
authors.lastname: Sahu
authors.forename: Leland R
authors.initials: LR
authors.lastname: Widger
authors.forename: Matthew G
authors.initials: MG
authors.lastname: Quesne
authors.forename: Sam P
authors.initials: SP
authors.lastname: de Visser
authors.forename: Hirotoshi
authors.initials: H
authors.lastname: Matsumura
authors.forename: Pierre
authors.initials: P
authors.lastname: Moënne-Loccoz
authors.forename: Maxime A
authors.initials: MA
authors.lastname: Siegler
authors.forename: David P
authors.initials: DP
authors.lastname: Goldberg
mesh_terms: D000577:Amides / Q000737:chemistry; D040761:Biomimetic Materials / Q000737:chemistry*; D005296:Ferrous Compounds / Q000737:chemistry*; D006900:Hydroxylation; D008024:Ligands; D008958:Models, Molecular; D011789:Quantum Theory
chemical_list: D000577:Amides; D005296:Ferrous Compounds; D008024:Ligands