2014
DOI: 10.1038/ncomms4046
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Abstract: Synthetically useful hydrocarbon oxidations are catalysed by bio-inspired non-heme iron complexes using hydrogen peroxide as oxidant, and carboxylic acid addition enhances their selectivity and catalytic efficiency. Talsi has identified a low-intensity g ¼ 2.7 electron paramagnetic resonance signal in such catalytic systems and attributed it to an oxoiron(V)-carboxylate oxidant. Herein we report the use of Fe II (TPA*) (TPA* ¼ tris (3,5-dimethyl-4-methoxypyridyl-2-methyl)amine) to generate this intermediate in… Show more

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Cited by 87 publications
(140 citation statements)
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“…Most importantly, Mossbauer studies revealed an iron center with a quadrupole splitting ΔE Q = 2.60(5) mm/s and an isomer shift δ = +0.17(3) mm/s, parameters consistent only with an S = 1/2 iron(III) center. These values were well reproduced by DFT calculations on [(TPA*)Fe III (κ 2 -OOC(O)R)] 2+ with the O atom of the terminal peroxo ligand bound trans to the TPA* amine donor(Figure 9) 32. …”
supporting
confidence: 60%
See 1 more Smart Citation
“…Most importantly, Mossbauer studies revealed an iron center with a quadrupole splitting ΔE Q = 2.60(5) mm/s and an isomer shift δ = +0.17(3) mm/s, parameters consistent only with an S = 1/2 iron(III) center. These values were well reproduced by DFT calculations on [(TPA*)Fe III (κ 2 -OOC(O)R)] 2+ with the O atom of the terminal peroxo ligand bound trans to the TPA* amine donor(Figure 9) 32. …”
supporting
confidence: 60%
“…32 Replacement of the TPA ligand with its more electrondonating TPA* analog (Chart 1) gave rise to an intermediate designated as 1b* with sharper EPR signals at g = 2.58, 2.42, 1.70 from the reaction of (TPA*)Fe III −OOH (1a*) and AcOH (Figure 8). 32 Species 1b* also exhibited an intense chromophore at 460 nm that tracked the formation and decay of the g max = 2.58 EPR signals ( Figure S1). This species could also be generated in similar yields using 1*/AcOOH or 1*/mCPBA, combinations analogous to those used by Talsi to generate 1b.…”
Section: ■ the Remarkable Effect Of A Carboxylicmentioning
confidence: 99%
“…Many examples of monoiron(III)-hydroperoxo species have been reported, with typical syntheses involving reactions of Fe(III) precursors with H 2 O 2 [145,195,196]. The reactivity of such intermediates prepared in this way has come under particular scrutiny of late [197] due to the discovery of selective catalytic oxidations by iron complexes with H 2 O 2 [198][199][200]. More rare is the identification of monoiron(III)-hydroperoxo species from reactions of Fe(II) complexes with O 2 via processes that directly model dioxygen activation by metalloprotein active sites.…”
Section: Monoiron Superoxo and Hydroperoxo Complexesmentioning
confidence: 99%
“…The Mn complexes performed up to 970 catalytic cycles. Cyclohexanol/cyclohexanone ratios of 4.9-5.1 and high 3 • /2 • selectivities of adamantane oxidation (40)(41)(42)(43)(44)(45)(46)(47)(48)(49) pointed to a metal-mediated rather than a radical-driven oxidation mechanism. The high sensitivity of the oxygen-transferring species to electronic effects, and high selectivity and stereospecificity (>99% RC) in the oxidation of cis-1,2-dimethylcyclohexane also support the metal-mediated oxidation mechanism [81].…”
Section: C-h Oxidations With H2o2 In the Presence Of Mn Complexes Witmentioning
confidence: 99%
“…In competitive contribution, Costas and co-workers showed that the introduction of additional steric crowd at the pyridine moieties, as well as manipulating with the symmetry of the chiral ligand can divert the oxidation selectivity from 3° C(sp 3 )-H bonds to stronger 2° C(sp 3 )-H bonds, which is critical for the selective oxygenation of complex molecules such as natural products [35][36][37][38]. The mechanism of non-heme iron catalyzed oxidations has been extensively studied experimentally [39]; it has now been accepted that the C-H oxidation proceeds via the classical rebound mechanism [40] (Figure 1), with participation of the elusive oxoperferryl species [41][42][43][44][45][46][47][48][49]. In contrast to non-heme Fe complexes, the catalytic activity (as well as the mechanism of catalytic action) of structurally related Mn complexes have so far been much less studied.…”
Section: Introductionmentioning
confidence: 99%