Reductive Nitric Oxide Coupling at a Dinickel Core: Isolation of a Key cis ‐Hyponitrite Intermediate en route to N 2 O Formation

Reductive coupling of nitric oxide (NO) to give N 2 O is an important reaction in the global nitrogen cycle. Here, a dinickel(II) dihydride complex 1 that releases H 2 upon substrate binding and serves as a masked dinickel(I) scaffold is shown to reductively couple two molecules of NO within the bimetallic cleft. The resulting hyponitrite complex 2 features an unprecedented cis ‐[N 2 O 2 ] 2− binding mode that has been computationally proposed as a key intermediate in flavodiiron nitric oxide reductases (FNORs). NMR and DFT evidence indicate facile rotational fluxionality of the [N 2 O 2 ] 2− unit, which allows to access an isomer that is prone to N 2 O release. Protonation of 2 is now found to trigger rapid N 2 O evolution and formation of a hydroxido bridged complex, reminiscent of FNOR reactivity. This work provides fundamental insight into the biologically relevant reductive coupling of two NO molecules and the subsequent trajectory towards N 2 O formation at bimetallic sites.