Wenjie Tao, research associate, Shanghai Institute of Organic Chemistry (China)
Shiyu Zhang, faculty mentor
Approximately 25% of energy production in the United States is derived from natural gas, primarily composed of methane. Due to its low energy density by volume, methane needs to be transferred as compressed gas, which is energy intensive and expensive. Developing a strategy to convert methane to liquid methanol fuel can provide the foundation of efficient utilization of natural gas. However, this transformation is catalyzed by limited systems because of the high bond strength of the C-H bond.
One system for methane mono oxygenation is copper-exchanged zeolites, for which the Cu(II)-O-Cu(II) moiety has been proposed as the active site. I developed a new dicopper synthetic model that activates both nitrite and nitric oxide under anaerobic conditions to afford the first fully characterized dicopper (II,III) -oxo, -nitrosyl species. This species can be further applied to activate the benzylic C-H bond in isochroman, furnishing the C-O coupled product 1-isochromanone.
Given that dicopper sites in proteins/enzymes could participate in the oxidation/oxygenation of many biological substrates, our findings suggest a new anaerobic pathway to access a dicopper mu-oxo moiety that may engage in challenging biochemical oxidation processes. This work has been published in Journal of American Chemical Society.