Department of Chemistry, Indian Institute of Science Education and Research (IISER), Tirupati 517507, India.
Division of Chemistry & Toxicology, WTL - Clean & Renewable Energy Pvt Ltd, New Delhi, India.
Dalton Trans. 2023 Apr 25;52(16):5095-5100. doi: 10.1039/d3dt00159h.
Here, we report the nitric oxide dioxygenation (NOD) reactions of two Mn-peroxo (M-O) complexes, [(3PYENMe)Mn(O)] (1) and [(N3PY)Mn(O)] (2), bearing pentadentate ligands. Complexes 1 and 2 give Mn-nitrate (Mn-NO) complexes (3 and 4) when reacted with nitric oxide (NO), respectively. The mechanistic study explored by using 2,4-di--butylphenol (2,4-DTBP) suggested that the NOD reaction of 1 and 2 occurs a presumed Mn-peroxynitrite ([Mn-PN], [Mn-ONOO]) intermediate. Tracking the source of N atoms using NO revealed that the N-atoms in Mn-NO (3 and 4) are derived from the NO moiety. Furthermore, we have explored the M-O regeneration from NOD products (3 and 4), and we have observed the formation of M-O complexes (1 and 2) upon treatment with KO or HO/triethylamine (TEA), respectively.
在这里，我们报告了两种锰过氧（M-O）配合物，[(3PYENMe)Mn(O)]（1）和[(N3PY)Mn(O)]（2），它们带有五齿配体，其一氧化氮二氧（NOD）反应。当与一氧化氮（NO）反应时，配合物 1 和 2 分别得到锰硝酸盐（Mn-NO）配合物（3 和 4）。通过使用 2,4-二--丁基苯酚（2,4-DTBP）进行的机理研究表明，1 和 2 的 NOD 反应发生在假定的锰过氧亚硝酸盐（[Mn-PN]，[Mn-ONOO]）中间体中。通过跟踪使用 NO 追踪 N 原子的来源，发现 Mn-NO（3 和 4）中的 N 原子来自 NO 部分。此外，我们还探索了从 NOD 产物（3 和 4）中再生 M-O 的过程，并观察到用 KO 或 HO/三乙胺（TEA）处理后分别形成 M-O 配合物（1 和 2）。
