Nitrate Upcycling Mediated by Organonickel Catalysis

Nitrogen oxides (NO_x) are major environmental pollutants and to neutralize this long-term environmental threat, new catalytic methods are needed. Although there are biological denitrification processes involving four different enzymatic reactions to convert nitrate (NO₃ ^-) into dinitrogen (N₂), it is unfortunately difficult to apply in industry due to the complexity of the processes. In particular, nitrate is difficult to functionalize because of its chemical stability. Thus, there is no organometallic catalysis to convert nitrate into useful chemicals. Herein, we present a nickel pincer complex that is effective as a bifunctional catalyst to stepwise deoxygenate NO₃ ^- by carbonylation and further through C-N coupling. By using this nickel catalysis, nitrate salts can be selectively transformed into various oximes (>20 substrates) with excellent conversion (>90 %). Here, we demonstrate for the first time that the highly inert nitrate ion can be functionalized to produce useful chemicals by a new organonickel catalysis. Our results show that the NO_x conversion and utilization (NCU) technology is a successful pathway for environmental restoration coupled with value-added chemical generation.