Dataset Information

H₂O₂ Oxidation by Fe^III-OOH Intermediates and Its Effect on Catalytic Efficiency.

ABSTRACT: The oxidation of the C-H and C=C bonds of hydrocarbons with H₂O₂ catalyzed by non-heme iron complexes with pentadentate ligands is widely accepted as involving a reactive Fe^IV=O species such as [(N4Py)Fe^IV=O]²⁺ formed by homolytic cleavage of the O-O bond of an Fe^III-OOH intermediate (where N4Py is 1,1-bis(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)methanamine). We show here that at low H₂O₂ concentrations the Fe^IV=O species formed is detectable in methanol. Furthermore, we show that the decomposition of H₂O₂ to water and O₂ is an important competing pathway that limits efficiency in the terminal oxidant and indeed dominates reactivity except where only sub-/near-stoichiometric amounts of H₂O₂ are present. Although independently prepared [(N4Py)Fe^IV=O]²⁺ oxidizes stoichiometric H₂O₂ rapidly, the rate of formation of Fe^IV=O from the Fe^III-OOH intermediate is too low to account for the rate of H₂O₂ decomposition observed under catalytic conditions. Indeed, with excess H₂O₂, disproportionation to O₂ and H₂O is due to reaction with the Fe^III-OOH intermediate and thereby prevents formation of the Fe^IV=O species. These data rationalize that the activity of these catalysts with respect to hydrocarbon/alkene oxidation is maximized by maintaining sub-/near-stoichiometric steady-state concentrations of H₂O₂, which ensure that the rate of the H₂O₂ oxidation by the Fe^III-OOH intermediate is less than the rate of the O-O bond homolysis and the subsequent reaction of the Fe^IV=O species with a substrate.

SUBMITTER: Chen J

PROVIDER: S-EPMC6179451 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature

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Publications

H2O2 Oxidation by FeIII-OOH Intermediates and Its Effect on Catalytic Efficiency.

Chen Juan J Draksharapu Apparao A Angelone Davide D Unjaroen Duenpen D Padamati Sandeep K SK Hage Ronald R Swart Marcel M Duboc Carole C Browne Wesley R WR

ACS catalysis 20180906 10

The oxidation of the C-H and C=C bonds of hydrocarbons with H2O2 catalyzed by non-heme iron complexes with pentadentate ligands is widely accepted as involving a reactive FeIV=O species such as [(N4Py)FeIV=O]2+ formed by homolytic cleavage of the O-O bond of an FeIII-OOH intermediate (where N4Py is 1,1-bis(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)methanamine). We show here that at low H2O2 conce ...[more]

PMID: 30319886

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Project description:Studies on molecular co-crystal type materials are important in the design and preparation of easy-to-absorb drugs, non-centrosymmetric, and chiral crystals for optical performance, liquid crystals, or plastic phases. From a fundamental point of view, such studies also provide useful information on various supramolecular synthons and molecular ordering, including metric parameters, molecular matching, energetical hierarchy, and combinatorial potential, appealing to the rational design of functional materials through structure-properties-application schemes. Co-crystal salts involving anionic d-metallate coordination complexes are moderately explored (compared to the generality of co-crystals), and in this context, we present a new series of isomorphous co-crystalline salts (PPh4)3[M(CN)6](H3PG)2·2MeCN (M = Cr, 1; Fe, 2; Co 3; H3PG = phloroglucinol, 1,3,5-trihydroxobenzene). In this study, 1-3 were characterized experimentally using SC XRD, Hirshfeld analysis, ESI-MS spectrometry, vibrational IR and Raman, 57Fe Mössbauer, electronic absorption UV-Vis-NIR, and photoluminescence spectroscopies, and theoretically with density functional theory calculations. The two-dimensional square grid-like hydrogen-bond {[M(CN)6]3-;(H3PG)2}∞ network features original {[M(CN)6]3-;(H3PG)4} supramolecular cis-bis(chelate) motifs involving: (i) two double cyclic hydrogen bond synthons M(-CN⋅⋅⋅HO-)2Ar, {[M(CN)6]3-;H2PGH}, between cis-oriented cyanido ligands of [M(CN)6]3- and resorcinol-like face of H3PG, and (ii) two single hydrogen bonds M-CN⋅⋅⋅HO-Ar, {[M(CN)6]3-;HPGH2}, involving the remaining two cyanide ligands. The occurrence of the above tectonic motif is discussed with regard to the relevant data existing in the CCDC database, including the multisite H-bond binding of [M(CN)6]3- by organic species, mononuclear coordination complexes, and polynuclear complexes. The physicochemical and computational characterization discloses notable spectral modifications under the regime of an extended hydrogen bond network.

Project description:Kinetic studies aimed at determining the most probable mechanism for the proton-dependent [Fe(II)(S(Me2)N(4)(tren))](+) (1) promoted reduction of superoxide via a thiolate-ligated hydroperoxo intermediate [Fe(III)(S(Me2)N(4)(tren))(OOH)](+) (2) are described. Rate laws are derived for three proposed mechanisms, and it is shown that they should conceivably be distinguishable by kinetics. For weak proton donors with pK(a(HA)) > pK(a(HO(2))) rates are shown to correlate with proton donor pK(a), and display first-order dependence on iron, and half-order dependence on superoxide and proton donor HA. Proton donors acidic enough to convert O(2)(-) to HO(2) (in tetrahydrofuran, THF), that is, those with pK(a(HA)) < pK(a(HO(2))), are shown to display first-order dependence on both superoxide and iron, and rates which are independent of proton donor concentration. Relative pK(a) values were determined in THF by measuring equilibrium ion pair acidity constants using established methods. Rates of hydroperoxo 2 formation displays no apparent deuterium isotope effect, and bases, such as methoxide, are shown to inhibit the formation of 2. Rate constants for p-substituted phenols are shown to correlate linearly with the Hammett substituent constants ?(-). Activation parameters ((?H(++) = 2.8 kcal/mol, ?S(++) = -31 eu) are shown to be consistent with a low-barrier associative mechanism that does not involve extensive bond cleavage. Together, these data are shown to be most consistent with a mechanism involving the addition of HO(2) to 1 with concomitant oxidation of the metal ion, and reduction of superoxide (an "oxidative addition" of sorts), in the rate-determining step. Activation parameters for MeOH- (?H(++) = 13.2 kcal/mol and ?S(++) = -24.3 eu), and acetic acid- (?H(++) = 8.3 kcal/mol and ?S(++) = -34 eu) promoted release of H(2)O(2) to afford solvent-bound [Fe(III)(S(Me2)N(4)(tren))(OMe)](+) (3) and [Fe(III)(S(Me2)N(4)(tren))(O(H)Me)](+) (4), respectively, are shown to be more consistent with a reaction involving rate-limiting protonation of an Fe(III)-OOH, than with one involving rate-limiting O-O bond cleavage. The observed deuterium isotope effect (k(H)/k(D) = 3.1) is also consistent with this mechanism.

Dataset Information

H₂O₂ Oxidation by Fe^III-OOH Intermediates and Its Effect on Catalytic Efficiency.

Publications

H<sub>2</sub>O<sub>2</sub> Oxidation by Fe<sup>III</sup>-OOH Intermediates and Its Effect on Catalytic Efficiency.

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