Methane Diversification Through Tandem Photocatalysis

Methane is the simplest C1 hydrocarbon, yet it suffers from limited reactivity that prevents broad synthetic utility. However, expanding synthetic applications that use methane as a building block is of great interest due to the potential simplicity, efficient atom economy, and being a new methylation mechanism. Thus, we will expand greatly on the established use of Rh porphyrins for methane activation and C-H bond cleavage in a way to photocatalytically generate methyl radicals. These radicals will then be captured by various means, including at boron or nickel species for subsequent reactivity. We will investigate methane oxidation into methanol, methane cross-coupling reactions, and methane carboxylation into acetic acid relying on Si, Ni, and Ir catalysts working in tandem with Rh. These studies will elucidate new methane synthetic chemistry, which will be of great interest to synthesis, medicinal, energy, and commodity communities.