由{Fe(NO)}-{Fe(NO)}双核二亚硝酰基铁配合物引发的NO到[NO]再到NO的转化
NO-to-[NO]-to-NO Conversion Triggered by {Fe(NO)}-{Fe(NO)} Dinuclear Dinitrosyl Iron Complex.
作者信息
Wu Wun-Yan, Hsu Chia-Ning, Hsieh Chieh-Hsin, Chiou Tzung-Wen, Tsai Ming-Li, Chiang Ming-Hsi, Liaw Wen-Feng
机构信息
Department of Chemistry and Frontier Research Center of Fundamental and Applied Science of Matters , National Tsing Hua University , Hsinchu 30013 , Taiwan.
Department of Chemistry , National Sun Yat-sen University , Kaohsiung 80424 , Taiwan.
出版信息
Inorg Chem. 2019 Aug 5;58(15):9586-9591. doi: 10.1021/acs.inorgchem.9b01635. Epub 2019 Jul 11.
Flavodiiron nitric oxide reductases (FNORs) evolved in some pathogens are known to detoxify NO via two-electron reduction to NO to mitigate nitrosative stress. In this study, we describe how the electronically localized {Fe(NO)}-{Fe(NO)} dinuclear dinitrosyl iron complex (dinuclear DNIC) [(NO)Fe(μ-bdmap)Fe(NO)(THF)] () (bdmap = 1,3-bis(dimethylamino)-2-propanolate) can induce a reductive coupling of NO to form hyponitrite-coordinated tetranuclear DNIC, which then converts to NO. Upon the addition of 1 equiv of NO into the dinuclear {Fe(NO)}-{Fe(NO)} DNIC , the proposed side-on-bound [NO]-bridged [(NO)Fe(μ-bdmap)(κ-NO) Fe(NO)] intermediate may facilitate intermolecular (O)N-N(O) bond coupling to yield the paramagnetic tetranuclear quadridentate -hyponitrite-bound {(NO)Fe(μ-bdmap)Fe(NO)} that transforms to [Fe(NO)(μ-bdmap)], along with the release of NO upon Hbdmap (1,3-bis(dimethylamino)-2-propanol) added.
已知在一些病原体中进化出的黄素二铁一氧化氮还原酶（FNORs）可通过双电子还原将NO解毒为N₂O，以减轻亚硝化应激。在本研究中，我们描述了电子定域的{Fe(NO)}-{Fe(NO)}双核二亚硝酰基铁配合物（双核DNIC）[(NO)Fe(μ-bdmap)Fe(NO)(THF)]（ ）（bdmap = 1,3-双（二甲氨基）-2-丙醇盐）如何诱导NO进行还原偶联形成连二次硝酸根配位的四核DNIC，然后其再转化为N₂O。向双核{Fe(NO)}-{Fe(NO)} DNIC 中加入1当量的NO后，推测的侧基结合的[NO]桥连中间体[(NO)Fe(μ-bdmap)(κ-NO) Fe(NO)]可能促进分子间（O）N-N（O）键偶联，生成顺磁性的四核四齿连二次硝酸根结合的{(NO)Fe(μ-bdmap)Fe(NO)}，其转化为[Fe(NO)(μ-bdmap)]，同时在加入Hbdmap（1,3-双（二甲氨基）-2-丙醇）后释放出N₂O。
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