Alkane oxidation catalyzed by .mu.-oxo-bridged diferric complexes: a structure/reactivity correlation study

Ménage, Stéphane; Vincent, Jean‐Marc; Lambeaux, Claude; Chottard, Geneviève; Grand, André; Fontecave, Marc

doi:10.1021/ic00074a019

Cited by 163 publications

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“…[15,27] The selectivity for the oxidation at the tertiary position is higher than the average value of 2.7 found for Gif-type oxidations. [20] In the presence of t-BuOOH the oxidation of cyclohexene afforded cyclohexenol and cyclohexenone as major products (62.0%), together with a small amount (5.2%) of the epoxide product (entry 2).When styrene was used as substrate, the aliphatic product benzaldehyde was detected by GC analysis as a major product (entry 3).…”

Section: -Oxo Diiron(iii) Complex With An N-pyridylmethyl-nn-bis(4-mmentioning

confidence: 64%

“…The ORTEP drawing of the cation of 1 is shown in (5) • , respectively. [7,15] The linear Fe-O-Fe structure of complex 1 might be caused by the significant π -π stacking interaction between the two parallel aromatic rings of the two ligands in one molecule. The inter-ligand π -stacking interaction between the two halves of the molecule may also play a role in the stabilization of the singly oxo-bridged diiron complex.…”

Section: Resultsmentioning

confidence: 99%

“…m+ /t-BuOOH (H 2 O 2 ) (TPA = tris(2-pyridylmethyl)amine, X = Br, Cl, H 2 O), [10 -13] [Fe 2 O(L) 4 X n ] m+ /t-BuOOH [where L = bipyridine, 4,4 -(Me) 2 -bipy, phen; X = H 2 O, Cl], [14,15] [16] [Fe 2 O(salen) 2 ]/2-mercaptoethanol/O 2 ; [17] [18,19] [Fe 2 O(bbp) 2 (MeOH) 2 (NO 3 ) 2 ] (NO 3 ) 2 /t-BuOOH (H 2 O 2 ) (bbp = 2,6-bis(N-methylbenzimidazol-2-yl)pyridine), [20] [21] have been reported by different research groups.…”

Section: ]mentioning

confidence: 99%

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Synthesis and structure of a µ‐oxo diiron(III) complex with an N‐pyridylmethyl‐N,N‐bis(4‐methylbenzimidazol‐2‐yl)amine ligand and its catalytic property for hydrocarbon oxidation

Sun

Wang

et al. 2008

Applied Organom Chemis

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A µ-oxo diiron(III) complex [{Fe(pbba)Cl} 2 (µ-O)]Cl 2 (1, pbba = N-pyridylmethyl-N,N-bis(4-methylbenzimidazol-2-yl)amine) bearing multi-imidazolyl motifs was synthesized and characterized by X-ray crystallography to closely mimic the structural features of methane monooxygenase. As shown by its X-ray crystal structure, complex 1 is a centrosymmetric dimer with an Fe-O-Fe angle of 180• , and pseudo-octahedral around each iron(III) center. The catalytic ability of title compound in the oxidation of alkane and alkene is investigated by employing tert-butylhydroperoxide and m-chloroperbenzoic acid as oxidants under mild conditions. The catalytic oxidation results showed that radical intermediate dominates the oxidation process.

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Section: -Oxo Diiron(iii) Complex With An N-pyridylmethyl-nn-bis(4-mmentioning

confidence: 64%

Section: Resultsmentioning

confidence: 99%

Section: ]mentioning

confidence: 99%

See 1 more Smart Citation

Synthesis and structure of a µ‐oxo diiron(III) complex with an N‐pyridylmethyl‐N,N‐bis(4‐methylbenzimidazol‐2‐yl)amine ligand and its catalytic property for hydrocarbon oxidation

Sun

Wang

et al. 2008

Applied Organom Chemis

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“…[5b,7c, 10,11] Reaction Conditions A Solvent acetonitrile and the oxidant solutions in acetonitrile were dried over MgSO 4 and filtered before use in order to control the water content. The concentration of the oxidant was not affected by this drying process, confirmed by iodometric titration.…”

Section: Methodsmentioning

confidence: 99%

In situ Formation of Peracetic Acid in Iron‐Catalyzed Epoxidations by Hydrogen Peroxide in the Presence of Acetic Acid

2004

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Iron complexes (tpa)Fe(OTf) 2 (1) and (bpmen)Fe(OTf) 2 (2) [tpa tris-(2-pyridylmethyl)-amine; bpmen N,N'-bis-(2-pyridylmethyl)-N,N'-dimethyl-1,2-ethylenediamine] were found to catalyze the in situ formation of AcOOH from H 2 O 2 and AcOH in the course of olefin oxidations. While oxidation of cyclooctene by H 2 O 2 catalyzed by 1 gives nearly equimolar epoxide and cis-diol products, introduction of AcOH to the reaction greatly enhances the selectivity for epoxidation. The resulting product distribution is nearly identical to that of cyclooctene oxidation by AcOOH catalyzed by 1. The in situ generation of AcOOH from H 2 O 2 and AcOH in epoxidation catalyzed by some iron complexes opens a possibility to attain AcOOH-type efficiency of epoxidation using H 2 O 2 as a terminal oxidant.

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“…For comparison: 38/28 ratios of 2.7, on average, have been found for Gif-type oxidations, [37] [38] and 11 ± 48 for oxidations with PhIO catalyzed by P450 mimics. [39] Thus the oxidant involved in [Fe(N4Py)-(CH 3 CN)](ClO 4 ) 2 /H 2 O 2 is not as reactive as hydroxyl radicals, but only slightly less so.…”

Section: Mechanistic Probes Of Alkane Hydroxylationmentioning

confidence: 99%

Catalytic Oxidation with a Non-Heme Iron Complex That Generates a Low-Spin FeIIIOOH Intermediate

et al. 2000

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The antitumor drug bleomycin (BLM) is proposed to act via a low-spin iron(III) hydroperoxide intermediate called "activated bleomycin". To gain more insight into the mechanistic aspects of catalytic oxidation by these intermediates we have studied the reactivity of [(N4Py)Fe(CH3CN)](ClO4)2 (1) (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) with excess H2O2. Under these conditions a transient purple species is generated, [(N4Py)FeOOH]2- (2), which has spectroscopic features and reactivity strongly reminiscent of activated bleomycin. The catalytic oxidation of alkanes such as cyclohexane, cyclooctane, and adamantane by 1 with H2O2 gave the corresponding alcohols and ketones in up to 31% yield. It was concluded, from the O2 sensitivity of the oxidation reactions, the formation of brominated products in the presence of methylene bromide, and the nonstereospecificity of the oxidation of cis- or trans-dimethylcyclohexane, that long-lived alkyl radicals were formed during the oxidations. Oxidation of alkenes did not afford the corresponding epoxides in good yields but resulted instead in allylic oxidation products in the case of cyclohexene, and cleavage of the double bond in the case of styrene. Addition of hydroxyl radical traps, such as benzene and acetone, led to only partial quenching of the reactivity. The kinetic isotope effects for cyclohexanol formation, ranging from 1.5 in acetonitrile to 2.7 in acetone with slow addition of H2O2, suggested the involvement of a more selective oxidizing species in addition to hydroxyl radicals. Monitoring the UV/Vis absorption of 2 during the catalytic reaction showed that 2 was the precursor for the active species. On the basis of these results it is proposed that 2 reacts through homolysis of the O-O bond to afford two reactive radical species: [(N4Py)Fe(IV)O]2+ and *OH. The comparable reactivity of 1 and Fe-BLM raises the possibility that they react through similar mechanistic pathways.

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Alkane oxidation catalyzed by .mu.-oxo-bridged diferric complexes: a structure/reactivity correlation study

Cited by 163 publications

References 0 publications

Synthesis and structure of a µ‐oxo diiron(III) complex with an N‐pyridylmethyl‐N,N‐bis(4‐methylbenzimidazol‐2‐yl)amine ligand and its catalytic property for hydrocarbon oxidation

Synthesis and structure of a µ‐oxo diiron(III) complex with an N‐pyridylmethyl‐N,N‐bis(4‐methylbenzimidazol‐2‐yl)amine ligand and its catalytic property for hydrocarbon oxidation

In situ Formation of Peracetic Acid in Iron‐Catalyzed Epoxidations by Hydrogen Peroxide in the Presence of Acetic Acid

Catalytic Oxidation with a Non-Heme Iron Complex That Generates a Low-Spin FeIIIOOH Intermediate

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