Alkane functionalization at ([mu]-Oxo)diiron(III) centers

Journal Article · Wed Oct 20 04:00:00 EDT 1993 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00074a017· OSTI ID:5188981

Leising, R A; Kim, J; Perez, M A; Que, L Jr ^[1]

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1. Univ. of Minnesota, Minneapolis, MN (United States)

The reactivity of ([mu]-oxo)diferric complexes with [sup t]BuOOH (TBHP) for the functionalization of alkanes in CH[sub 3]CN has been investigated as part of our efforts to model dinuclear sites in nonheme iron enzymes. [Fe[sub 2](TPA)[sub 2]O(OAc)](CIO[sub 4])[sub 3] (1) (TPA = tris(2-pyridylmethyl)amine, OAc = acetate) is an efficient catalyst for cyclohexane oxidation, affording cyclohexanol (A, 9 equiv), cyclohexanone (K, 11 equiv), and (tert-butylperoxy)cyclohexane (P, 16 equiv) in 0.25 h at ambient temperature and pressure under an argon atmosphere. The catalyst is remarkably robust, as indicated by the [sup 1]H NMR and UV-vis spectra of the reaction mixture during the catalytic reaction and by its ability to maintain its turnover efficiency with subsequent additions of oxidant. The catalytic mechanism for TBHP utilization was explored by observing the effects of varying the tripodal ligands on the ([mu]-oxo)([mu]-carboxylato)diferric catalysts and varying the bridge on Fe[sub 2]O(TPA)[sub 2] catalysts. The (A + K)/P ratio increased as the ligands became more electron donating. Solvent also played an important role in determining the partitioning of products between A + K and P, with benzonitrile favoring hydroxylated products at the expense of P and pyridine having the opposite effect. 49 refs., 2 figs., 3 tabs.

• OSTI ID: 5188981
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 115:21; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

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ACETONITRILE
ALCOHOLS
ALKANES
CATALYSIS
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
CYCLOALKANES
CYCLOHEXANE
CYCLOHEXANOL
CYCLOHEXANONE
DATA
DIMETHYL SULFIDE
ENZYMES
EXPERIMENTAL DATA
HYDROCARBONS
HYDROXY COMPOUNDS
HYDROXYLATION
INFORMATION
IRON COMPLEXES
KETONES
LIGANDS
MAGNETIC RESONANCE
MASS SPECTROSCOPY
NITRILES
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXIDATION
OXYGEN COMPOUNDS
PEROXIDES
PROTEINS
RADICALS
RESONANCE
SPECTROSCOPY
SULFIDES
SULFUR COMPOUNDS
TRANSITION ELEMENT COMPLEXES