A novel monomeric tetravalent manganese complex with the cross-bridged cyclam ligand 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane (Me2EBC), [Mn(IV)(Me2EBC)(OH)2](PF6)2, was synthesized by oxidation of Mn(II)(Me2EBC)Cl2 with H2O2 in the presence of NH4PF6)in aqueous solution. The X-ray crystal structure determination of this manganese(IV) compound revealed that it contains two rare terminal hydroxo ligands. EPR studies in dry acetonitrile at 77 K show two broad resonances at g = 1.96 and 3.41, indicating that the manganese(IV) exists as a high-spin d3 species. Resonance Raman (rR) spectra of this manganese(IV) species reveal that the dihydroxy moiety, Mn(IV)(OH)2, is also the dominant species in aqueous solution (pH < 7). pH titration provides two pK(a) values, 6.86(4) and 10.0(1), associated with stepwise removal of the last two oxygen-bound protons from [Mn(IV)(Me2EBC)(OH)2](2+). The cyclic voltammetry of this manganese(IV) complex in dry acetonitrile at 298 K demonstrates two reversible redox processes at +0.756 and -0.696 V (versus SHE) for the Mn4+/Mn3+ and Mn3+/Mn2+ couples, respectively. This manganese(IV) complex is relatively stable in weak acidic aqueous solution but easily degrades in basic solution to manganese(III) derivatives with an 88 +/- 1% yield.

Clarifying the difference in redox reactivity between the metal oxo and metal hydroxo moieties for the same redox active metal ion in identical structures and oxidation states, that is, M(n+)O and M(n+)-OH, contributes to the understanding of nature's choice between them (M(n+)O or M(n+)-OH) as key active intermediates in redox enzymes and electron transfer enzymes, and provides a basis for the design of synthetic oxidation catalysts. The newly synthesized manganese(IV) complex having two hydroxide ligands, [Mn(Me(2)EBC)(2)(OH)(2)](PF(6))(2), serves as the prototypic example to address this issue, by investigating the difference in the hydrogen abstracting abilities of the Mn(IV)O and Mn(IV)-OH functional groups. Independent thermodynamic evaluations of the O-H bond dissociation energies (BDE(OH)) for the corresponding reduction products, Mn(III)-OH and Mn(III)-OH(2), reveal very similar oxidizing power for Mn(IV)O and Mn(IV)-OH (83 vs 84.3 kcal/mol). Experimental tests showed that hydrogen abstraction proceeds at reasonable rates for substrates having BDE(CH) values less than 82 kcal/mol. That is, no detectable reaction occurred with diphenyl methane (BDE(CH) = 82 kcal/mol) for both manganese(IV) species. However, kinetic measurements for hydrogen abstraction showed that at pH 13.4, the dominant species Mn(Me(2)EBC)(2)(O)(2), having only Mn(IV)O groups, reacts more than 40 times faster than the Mn(IV)-OH unit in Mn(Me(2)EBC)(2)(OH)(2)(2+), the dominant reactant at pH 4.0. The activation parameters for hydrogen abstraction from 9,10-dihydroanthracene were determined for both manganese(IV) moieties: over the temperature range 288-318 K for Mn(IV)(OH)(2)(2+), DeltaH(double dagger) = 13.1 +/- 0.7 kcal/mol, and DeltaS(double dagger) = -35.0 +/- 2.2 cal K(-1) mol(-1); and the temperature range 288-308 K for for Mn(IV)(O)(2), DeltaH(double dagger) = 12.1 +/- 1.8 kcal/mol, and DeltaS(double dagger) = -30.3 +/- 5.9 cal K(-1) mol(-1).

Developing novel technologies to cleanup wastewater has attracted attention for a long while in academic and industrial communities not only for environmental issues but also for recycling water sources. This work demonstrates that bicarbonate-activated H2O2 can be applied as a novel oxidant source in pollutant degradation. Using a supported cobalt catalyst, bicarbonate-activated H2O2 can efficiently degrade various dyes and phenol at ambient temperature. Because the reaction media remains weakly basic during degradation, the cobalt leaching from the solid catalyst has been efficiently avoided and the lifetime of the catalyst can be extended to above 180 h without significant activity loss in a fixed-bed test. Different scavengers, including ascorbic acid, t-butanol, sodium azide, benzoquinone, and tiron, have been tested to identify the active species, which may be involved in pollutant degradation, and it was found that singlet oxygen and the carbonate radical may play a key role in the degradation process.

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Distinctive mechanistic pathways account for the remarkable selectivity of a molecularly designed and robust manganese catalyst, Mn(Me2EBC)Cl2, whose activated form has been isolated and thoroughly characterized. In keeping with the existence of two activated catalytic functional groups, MnIV(OH)2 2+ (BDEOH = 83.0 kcal/mol) and MnIV(O)OH+ (BDEOH = 84.3 kcal/mol), two distinctive Polanyi correlations are observed, the latter being over 10-fold more rapid despite their similarity. Remarkably, only relatively weak C−H bonds (≤∼82 kcal/mol) suffer hydrogen abstraction by either group, with the stoppage occurring at substrate BDE CH ≥ catalyst BDE OH . Earlier studies established a selective Lewis acid mechanism as the dominant oxygen atom insertion pathway for this catalyst. These two pathways (hydrogen abstraction and oxygen atom transfer) dominate the oxidation reactions catalyzed by these systems, accounting for the moderate oxidizing power and associated selectivity of Mn(Me2EBC)Cl2 in H2O2 oxidations.

Using heteropolyacid and copper(ii) as catalysts, renewable furfural has been successfully transformed to maleic anhydride and biologically important 5-acetoxyl-2(5H)-furfuran.

Multiple transition metal functional groups including metaloxo, hydroxo, and hydroperoxide groups play significant roles in various biological and chemical oxidations such as electron transfer, oxygen transfer, and hydrogen abstraction. Further studies that clarify their oxidative relationships and the relationship between their reactivity and their physicochemical properties will expand our ability to predict the reactivity of the intermediate in different oxidative events. As a result researchers will be able to provide rational explanations of poorly understood oxidative phenomena and design selective oxidation catalysts. This Account summarizes results from recent studies of oxidative relationships among manganese(IV) molecules that include pairs of hydroxo/oxo ligands. Changes in the protonation state may simultaneously affect the net charge, the redox potential, the metal-oxygen bond order (M-O vs M═O), and the reactivity of the metal ion. In the manganese(IV) model system, [Mn(IV)(Me(2)EBC)(OH)(2)](PF(6))(2), the Mn(IV)-OH and Mn(IV)═O moieties have similar hydrogen abstraction capabilities, but Mn(IV)═O abstracts hydrogen at a more than 40-fold faster rate than the corresponding Mn(IV)-OH. However, after the first hydrogen abstraction, the reduction product, Mn(III)-OH(2) from the Mn(IV)-OH moiety, cannot transfer a subsequent OH group to the substrate radical. Instead the Mn(III)-OH from the Mn(IV)═O moiety reforms the OH group, generating the hydroxylated product. In the oxygenation of substrates such as triarylphosphines, the reaction with the Mn(IV)═O moiety proceeds by concerted oxygen atom transfer, but the reaction with the Mn(IV)-OH functional group proceeds by electron transfer. In addition, the manganese(IV) species with a Mn(IV)-OH group has a higher redox potential and demonstrates much more facile electron transfer than the one that has the Mn(IV)═O group. Furthermore, an increase in the net charge of the Mn(IV)-OH further accelerates its electron transfer rate. But its influence on hydrogen abstraction is minor because charge-promoted electron transfer does not enhance hydrogen abstraction remarkably. The Mn(IV)-OOH moiety with an identical coordination environment is a more powerful oxidant than the corresponding Mn(IV)-OH and Mn(IV)═O moieties in both hydrogen abstraction and oxygen atom transfer. With this full understanding of the oxidative reactivity of the Mn(IV)-OH and Mn(IV)═O moieties, we have clarified the correlation between the physicochemical properties of these active intermediates, including net charge, redox potential, and metal-oxygen bond order, and their reactivities. The reactivity differences between the metal oxo and hydroxo moieties on these manganese(IV) functional groups after the first hydrogen abstraction have provided clues for understanding their occurrence and functions in metalloenzymes. The P450 enzymes require an iron(IV) oxo form rather than an iron(IV) hydroxo form to perform substrate hydroxylation. However, the lipoxygenases use an iron(III) hydroxo gro...

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