title: Nonheme FeIVO complexes that can oxidize the C-H bonds of cyclohexane at room temperature.
abstract: Nonheme oxoiron(IV) complexes of two pentadentate ligands, N4Py (N,N-bis(2-pyridylmethyl)-bis(2-pyridyl)methylamine) and Bn-tpen (N-benzyl-N,N',N'-tris(2-pyridylmethyl)-1,2-diaminoethane), have been generated and found to have spectroscopic properties similar to the closely related tetradentate TPA (tris(2-pyridylmethyl)amine) complex reported earlier. However, unlike the TPA complex, the pentadentate complexes have a considerable lifetime at room temperature. This greater thermal stability has allowed the hydroxylation of alkanes with C-H bonds as strong as 99.3 kcal/mol to be observed at room temperature. Furthermore, a large deuterium KIE value is found in the oxidation of ethylbenzene. These observations lend strong credence to postulated mechanisms of mononuclear nonheme iron enzymes that invoke the intermediacy of oxoiron(IV) species.
authors.affiliation: Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, Minnesota 55455, USA.
authors.forename: József
authors.initials: J
authors.lastname: Kaizer
authors.forename: Eric J
authors.initials: EJ
authors.lastname: Klinker
authors.forename: Na Young
authors.initials: NY
authors.lastname: Oh
authors.forename: Jan-Uwe
authors.initials: JU
authors.lastname: Rohde
authors.forename: Woon Ju
authors.initials: WJ
authors.lastname: Song
authors.forename: Audria
authors.initials: A
authors.lastname: Stubna
authors.forename: Jinheung
authors.initials: J
authors.lastname: Kim
authors.forename: Eckard
authors.initials: E
authors.lastname: Münck
authors.forename: Wonwoo
authors.initials: W
authors.lastname: Nam
authors.forename: Lawrence
authors.initials: L
authors.lastname: Que
mesh_terms: D040761:Biomimetic Materials / Q000737:chemistry; D003510:Cyclohexanes / Q000737:chemistry*; D005029:Ethylenediamines / Q000737:chemistry; D007501:Iron / Q000737:chemistry*; D058085:Iron Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry; D013696:Temperature
chemical_list: D003510:Cyclohexanes; D005029:Ethylenediamines; D058085:Iron Compounds; C431844:N4Py compound; D011725:Pyridines; C066317:ferryl iron; D007501:Iron; D010100:Oxygen