Reductive Nitric Oxide Coupling at a Dinickel Core: Isolation of a Key cis ‐Hyponitrite Intermediate en route to N 2 O Formation
| Autor: | Franc Meyer, Max C. Holthausen, Sebastian Dechert, Serhiy Demeshko, Eleonora Ferretti |
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| Rok vydání: | 2019 |
| Předmět: |
010405 organic chemistry
Stereochemistry Substrate (chemistry) chemistry.chemical_element Protonation General Medicine General Chemistry 010402 general chemistry 01 natural sciences Catalysis 0104 chemical sciences Nitric oxide chemistry.chemical_compound Nickel chemistry Hyponitrite Molecule Reactivity (chemistry) Bimetallic strip |
| Zdroj: | Angewandte Chemie International Edition. 58:1705-1709 |
| ISSN: | 1521-3773 1433-7851 |
| Popis: | Reductive coupling of nitric oxide (NO) to give N2 O is an important reaction in the global nitrogen cycle. Here, a dinickel(II) dihydride complex 1 that releases H2 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-[N2 O2 ]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 [N2 O2 ]2- unit, which allows to access an isomer that is prone to N2 O release. Protonation of 2 is now found to trigger rapid N2 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 N2 O formation at bimetallic sites. |
| Databáze: | OpenAIRE |
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