Das Sandip, Ghosh Somnath, Chandra Sahoo Subash, Kumar Pankaj
Department of Chemistry, Indian Institute of Science Education and Research (IISER) Tirupati 517507 India
Department of Chemistry, Punjab University Chandigarh Punjab India.
Chem Sci. 2020 Apr 24;11(19):5037-5042. doi: 10.1039/d0sc01572e.
Here, we report the nitric oxide monooxygenation (NOM) reactions of a Co-nitrosyl complex (, {Co-NO}) in the presence of mono-oxygen reactive species, , a base (OH, tetrabutylammonium hydroxide (TBAOH) or NaOH/15-crown-5), an oxide (O or NaO/15-crown-5) and water (HO). The reaction of with OH produces a Co-nitrito complex {, (Co-NO )} and hydrogen gas (H), the formation of a putative N-bound Co-nitrous acid intermediate (, {Co-NOOH}). The homolytic cleavage of the O-H bond of proposed [Co-NOOH] releases H a presumed Co-H intermediate. In another reaction, generates Co-NO when reacted with O an expected Co-nitro () intermediate. However, complex is found to be unreactive towards HO. Mechanistic investigations using N-labeled-NO and H-labeled-NaOH (NaOD) evidently revealed that the N-atom in Co-NO and the H-atom in H gas are derived from the nitrosyl ligand and OH moiety, respectively.
在此，我们报道了在单氧活性物种、碱（OH、氢氧化四丁铵（TBAOH）或NaOH/15-冠-5）、氧化物（O或NaO/15-冠-5）和水（H₂O）存在下，钴亚硝酰配合物（，{Co-NO}）的一氧化氮单加氧（NOM）反应。与OH反应生成钴亚硝酸根配合物{，(Co-NO₂)}和氢气（H₂），推测形成了一个N键合的钴亚硝酸中间产物（，{Co-NOOH}）。推测的[Co-NOOH]中O-H键的均裂释放出H₂和一个推测的Co-H中间产物。在另一个反应中，与O反应时生成Co-NO₃和一个预期的钴硝基（）中间产物。然而，发现配合物对H₂O无反应性。使用N标记的-NO和H标记的-NaOH（NaOD）进行的机理研究明显表明，Co-NO₂中的N原子和H₂气体中的H原子分别来自亚硝酰配体和OH部分。
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