Manganese complexes with polydentate quinol-containing ligands are found to catalyze the degradation of superoxide through inner-sphere mechanisms. The redox activity of the ligand stabilizes higher-valent manganese species.
Density functional theory and high-level ab initio electronic structure calculations are performed to study the mechanism of the partial oxidation of methane to methanol facilitated by the titled anionic transition metal atoms. The energy landscape for the overall reaction M − + N 2 O + CH 4 → M − + N 2 + CH 3 OH (M = Fe, Ni, Pd, Pt) is constructed for different reaction pathways for all four metals. The comparison with earlier experimental and theoretical results for cationic centers demonstrates the better performance of the metal anions. The main advantage is that anionic centers interact weakly with the produced methanol. This fact facilitates the fast removal of methanol from the catalytic center and prevents the overoxidation of methane. Moreover, a moderate or high energy barrier for the M − + CH 4 → HMCH 3 − reaction step is observed, which protects the metal center from deactivation. Future work should focus on the identification of proper ligands, which stabilize the negative charge on the metal (electronic factors) and prevent the formation of the global CH 3 MOH − minimum (steric factors). Finally, a composite electronic structure method (combining size extensive coupled clusters approaches and accurate multireference configuration interaction) is proposed for computationally demanding systems and is applied to Fe − .
COMPUTAtIONAL STUDIES are performed to show that metal oxide anionic complexes promote the CH4+N2O→CH3OH+N2 reaction with low activation barriers for the C-H activation and the formation of the CH3-OH bond....
Transition metal oxides have been extensively used in the literature for the conversion of methane to methanol. Despite the progress made over the past decades, no method with satisfactory performance...
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