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

Abstract

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.

Authors:
; ; ;  [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States)
Publication Date:
OSTI Identifier:
5188981
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society; (United States)
Additional Journal Information:
Journal Volume: 115:21; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
10 SYNTHETIC FUELS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CYCLOHEXANE; HYDROXYLATION; OXIDATION; ACETONITRILE; CATALYSIS; CYCLOHEXANOL; CYCLOHEXANONE; DIMETHYL SULFIDE; ENZYMES; EXPERIMENTAL DATA; IRON COMPLEXES; LIGANDS; MASS SPECTROSCOPY; NUCLEAR MAGNETIC RESONANCE; PEROXIDES; RADICALS; SPECTROSCOPY; ALCOHOLS; ALKANES; CHALCOGENIDES; CHEMICAL REACTIONS; COMPLEXES; CYCLOALKANES; DATA; HYDROCARBONS; HYDROXY COMPOUNDS; INFORMATION; KETONES; MAGNETIC RESONANCE; NITRILES; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; ORGANIC SULFUR COMPOUNDS; OXYGEN COMPOUNDS; PROTEINS; RESONANCE; SULFIDES; SULFUR COMPOUNDS; TRANSITION ELEMENT COMPLEXES; 100200* - Synthetic Fuels- Production- (1990-); 400201 - Chemical & Physicochemical Properties; 400102 - Chemical & Spectral Procedures

Citation Formats

Leising, R A, Kim, J, Perez, M A, and Que, L Jr. Alkane functionalization at ([mu]-Oxo)diiron(III) centers. United States: N. p., 1993. Web. doi:10.1021/ja00074a017.
Leising, R A, Kim, J, Perez, M A, & Que, L Jr. Alkane functionalization at ([mu]-Oxo)diiron(III) centers. United States. https://doi.org/10.1021/ja00074a017
Leising, R A, Kim, J, Perez, M A, and Que, L Jr. Wed . "Alkane functionalization at ([mu]-Oxo)diiron(III) centers". United States. https://doi.org/10.1021/ja00074a017.
@article{osti_5188981,
title = {Alkane functionalization at ([mu]-Oxo)diiron(III) centers},
author = {Leising, R A and Kim, J and Perez, M A and Que, L Jr},
abstractNote = {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.},
doi = {10.1021/ja00074a017},
url = {https://www.osti.gov/biblio/5188981}, journal = {Journal of the American Chemical Society; (United States)},
issn = {0002-7863},
number = ,
volume = 115:21,
place = {United States},
year = {1993},
month = {10}
}