One metal is enough: a nickel complex reduces nitrate anions to nitrogen gas.

A stepwise reduction sequence from nitrate to dinitrogen gas at a single nickel center was discovered. A PNP nickel scaffold (PNP- = N[2-P i Pr2-4-Me-C6H3]2) emerged as a universal platform for the deoxygenation of NO x substrates. In these reactions carbon monoxide acts as the oxygen acceptor and forms CO2 to provide the necessary chemical driving force. Whereas the first two oxygens are removed from the Ni-nitrate and Ni-nitrite complexes with CO, the deoxygenation of NO requires a disproportionation reaction with another NO molecule to form NO2 and N2O. The final deoxygenation of nitrous oxide is accomplished by the Ni-NO complex and generates N2 and Ni-NO2 in a relatively slow, but clean reaction. This sequence of reactions is the first example of the complete denitrification of nitrate at a single metal-site and suggests a new paradigm of connecting CO and NO x as an effective reaction pair for NO x removal.