Nickel-mediated N-N bond formation and N₂O liberation via nitrogen oxyanion reduction.

ABSTRACT: The syntheses of (DIM)Ni(NO₃)₂ and (DIM)Ni(NO₂)₂, where DIM is a 1,4-diazadiene bidentate donor, are reported to enable testing of bis boryl reduced N-heterocycles for their ability to carry out stepwise deoxygenation of coordinated nitrate and nitrite, forming O(Bpin)₂. Single deoxygenation of (DIM)Ni(NO₂)₂ yields the tetrahedral complex (DIM)Ni(NO)(ONO), with a linear nitrosyl and κ¹-ONO. Further deoxygenation of (DIM)Ni(NO)(ONO) results in the formation of dimeric [(DIM)Ni(NO)]₂, where the dimer is linked through a Ni-Ni bond. The lost reduced nitrogen byproduct is shown to be N₂O, indicating N-N bond formation in the course of the reaction. Isotopic labelling studies establish

SUBMITTER: Beagan DM 

PROVIDER: S-EPMC8356809 | biostudies-literature | 2021 Aug

REPOSITORIES: biostudies-literature