Nonheme FeIVO complexes that can oxidize the C-H bonds of cyclohexane at room temperature.
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.
Kaizer
József
J
Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, Minnesota 55455, USA.
Klinker
Eric J
EJ
Oh
Na Young
NY
Rohde
Jan-Uwe
JU
Song
Woon Ju
WJ
Stubna
Audria
A
Kim
Jinheung
J
Münck
Eckard
E
Nam
Wonwoo
W
Que
Lawrence
L
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
D003510:Cyclohexanes; D005029:Ethylenediamines; D058085:Iron Compounds; C431844:N4Py compound; D011725:Pyridines; C066317:ferryl iron; D007501:Iron; D010100:Oxygen