Methane Activation by CoOmn+ (n=0, 1, 2; m= 1, 2): Reactivity Parameters, Electronic Properties and Binding Energy Analysis

The need for renewal and more efficient energy resources has led to a great interest in carrying out studies aiming to find novel sources of energy, which are able to supply the growing global demand, and providing an eco‐friendly usage of natural resources. In this context, the usage of methane stands out as a promising energetic alternative, mostly due to vast reserves, low cost and less polluting fuel. Theoretical studies with B3LYP, CCSD (t) and ZORA−B3LYP methods were used to look into the catalytic properties of (CoOmn+ n= 0, 1, 2 and m=1, 2) in the methane C−H bond activation. According to the EDA results, the studied species presented two stabilizing factors for the global interaction energy, being the electrostatic ΔEelstat and orbital ΔEorb interactions. The HOMO and LUMO orbitals were also evaluated based on the molecular orbital diagrams for the monoxides and dioxides series. Regarding the oxidative insertion mechanism, the results demonstrate that the initial interaction between oxide and methane is of great relevance in its activation process, in which EBonding is benefited by the increasingly charge on the central metal. The high electron density regarding the oxides is meaningful for the reaction kinetics and the oxo ligands influence the thermodynamics of the reaction, becoming the DHA mechanism exergonic. Regarding the OHM mechanism, better kinetic conditions are found for CoO2++ and better thermodynamics for doubly charged cobalt monoxides and dioxides. Currently, there is an increasing need for novel energy sources, and the use of methane stands out as a promising alternative to help supply the global energy demand. In this work, computational methods were employed to look into the catalytic properties of cobalt oxides in the methane C−H bond activation. Different mechanisms were investigated in order to raise insights about the reactivity, selectivity and electronic structures of cobalt oxide prototypes. The methane catalytic functionalization has been a challenging task worldwide.