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Manganese (Mn) oxides, widely found in aquatic and terrestrial environments, play crucial roles in natural ecosystems and in environmental processes. Previously, it was believed that naturally abundant Mn oxides originated through biotically mediated processes. However, we have revealed the significance of photochemically induced abiotic oxidation of Mn2+(aq) to Mn(IV) oxides. This study further elucidates the photochemically induced co-oxidation of aqueous Mn2+ and cobalt (Co2+), which leads to the predominant formation of Mn(IV)–Co(III) oxide nanosheets. Both pair distribution function analysis and X-ray absorption spectra provide evidence that Co2+ is mainly oxidized to Co(III) within the plane of the Mn oxide structure, where it forms double-edge-sharing arrangements. Additionally, the initial concentration of Co2+ greatly influences the extent of Co incorporation within the final Mn–Co oxides and Mn oxidation states. Increased Co incorporation correlates with a higher concentration of oxygen vacancies within the Mn oxide structures, which reduces their band gap and significantly influences the reactivity of Mn oxides, governing their ability to participate in pollutant degradation and redox transformations. This study advances our understanding of the mechanism of formation of Co-incorporated Mn oxides in the natural environment and provides insights into their occurrence in the natural environment and their applications in environmental processes.
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Effects of structural cobalt on the stability and reactivity of hausmannite and manganite: Cobalt coordination chemistry and arsenite oxidation
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null (Ed.)Synthesis of complex organic molecules has relied heavily on the use of stoichiometric organometallic reagents. Strategies such as metal-catalyzed cycloisomerization bypass the need for these oftentimes harsh reagents and are valuable for constructing cyclic frameworks from simple unsaturated carbon sources. An important extension of this cyclization methodology is the incorporation of additional components accompanying the initial annulation. Through our studies we learned that cationic cobalt complexes can catalyze an intramolecular enyne cyclization, and subsequently form carbon-carbon bonds through intermolecular incorporation of feedstock alkenes into a presumed metallacycle intermediate. This strategy allows access to complex alicyclic and heterocyclic compounds from an earth abundant metal catalyst and readily available materials. Of note, is the complimentary reactivity and selectivity in this newly discovered cationic cobalt reaction manifold as compared to analogous rhodium and ruthenium catalysis. We discovered that product selectivity is dependent upon alkene identity, with activated alkenes and unactivated alkenes inserting into opposite sides of the cobaltacyclopentene intermediate. This remarkable selectivity provides access to two different motifs accompanying the cycle formed, either a linear diene or a styrene with a pendant functionalized acrylate. Over 25 different medicinally relevant pyrrolidines were accessed in this fashion and further elaborated on by post-synthetic modifications. In addition, the enantioselective variant of this reaction is also explored with selectivities up to 77% ee.more » « less
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null (Ed.)ZIF-8, Co-ZIF-8, and Zn/Co-ZIF-8 are utilized in adsorbing nitrogen (N 2 ), methane (CH 4 ), and carbon dioxide (CO 2 ) gases at temperatures between 25 and 55°C and pressures up to ~1 MPa. Equilibrium adsorption isotherms and adsorption kinetics are studied. The dual-site Langmuir equation is employed to correlate the nonisothermal adsorption equilibrium behavior. Generally, N 2 showed the lowest equilibrium adsorption quantity on the three samples, whereas CO 2 showed the highest equilibrium adsorption capacity. Amid the ZIF samples, the biggest adsorption quantities of N 2 and CH 4 were onto Zn/Co-ZIF-8, whereas the highest adsorption quantity of CO 2 was on ZIF-8. The isosteric heats of adsorbing these gases on ZIF-8, Co-ZIF-8, and Zn/Co-ZIF-8 were examined. Moreover, the overall mass transfer coefficients of adsorption at different temperatures were investigated.more » « less
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Litwack, G. (Ed.)Vitamin B12 is one of the most complex cofactors known, and this chapter will discuss current understanding with regards to the cobalt insertion step of its syntheses. Two total syntheses of vitamin B12 were reported in the 1970s, which remain two of the most exceptional achievements of natural product synthesis. In subsequent years, two distinct biosynthetic pathways were identified in aerobic and anaerobic organisms. For these biosynthetic pathways, selectivity for Co(II) over other divalent metal ions with similar ionic radii and coordination chemistry remains an open question with three competing hypotheses proposed: metal affinity, tetrapyrrole distortion, and product inhibition. A 20 step biosynthetic route to convert 5-aminolevulinic acid (ALA) to vitamin B12 was elucidated in aerobic organisms in the 1990s, where cobalt is inserted relatively late in the pathway by the CobNST multi-protein complex. This chapter includes a mechanistic proposal for this reaction, but the majority of the proposal is based upon analogy to the ChlDHI magnesium chelatase complex as critical data for the cobalt chelatase is lacking. Later, in the 2010s, a distinct 21 step pathway from ALA to vitamin B12 was reported in anaerobic organisms, where cobalt is inserted early in the pathway by the enzyme CbiK. A recent study strongly suggests that the cobalt affinity of CbiK is the origin of cobalt selectivity for CbiK, but several important mechanistic questions remain unanswered. In general, it is expected that significant insight into the cobalt insertion mechanisms of CobNST and CbiK could be derived from additional structural, spectroscopic, and computational data.more » « less
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1016/j.chemgeo.2021.120453
