Redox‐Neutral S ‐nitrosation Mediated by a Dicopper Center
Redox‐Neutral S ‐nitrosation Mediated by a Dicopper Center
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二铜中心介导的氧化还原 - 中性 S - 亚硝化
DOI：
10.1002/anie.202102589
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发表时间：
2021
期刊：
影响因子：
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通讯作者：
Zhang, Shiyu
中科院分区：
文献类型：
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作者：
Tao, Wenjie;Moore, Curtis E.;Zhang, Shiyu
硫醇在二铜（I，I）中心实现了氧化还原-中性-亚硝化反应。过量NO对迪铜（I，I）络合物的处理。和硫醇生成二铜（I，I）二硫代亚硝基硫醇络合物[CuICuI(RSNO)2]2+或二铜（I，I）单硫代亚硝基硫醇络合物[CuICuI(RSNO)]2+，它们极易释放RSNO，产率为88 - 94%。这种亚硝化反应是通过混合价态的2+物质[CuIICuIII(μ‐O)(μ‐NO)]进行的，它在基本的μ‐O位点使RS‐H去质子化，在μ‐NO位点使RS‐亚硝酸盐化。[CuIICuIII(μ‐O)(μ‐NO)]2+配合物也能使MeOH发生O‐亚硝化。一种罕见的[CuIICuII(μ‐NO)(OMe)]2+中间体被分离出来并进行了充分的表征，表明亚硝化可能是通过类似的[CuIICuII(μ‐NO)(SR)]2+中间体进行的。这种氧化还原和质子中性亚硝化过程是铜蓝蛋白在介导外部硫醇亚硝化过程中的第一个功能模型，对no /RSNO相互转化中的生物铜位点具有重要意义。
A redox‐neutralS‐nitrosation of thiol has been achieved at a dicopper(I,I) center. Treatment of dicopper (I,I) complex with excess NO.and thiol generates a dicopper (I,I) di‐S‐nitrosothiol complex [CuICuI(RSNO)2]2+or dicopper (I,I) mono‐S‐nitrosothiol complex [CuICuI(RSNO)]2+, which readily release RSNO in 88–94 % yield. TheS‐nitrosation proceeds by a mixed‐valence [CuIICuIII(μ‐O)(μ‐NO)]2+species, which deprotonates RS‐H at the basic μ‐O site and nitrosates RS−at the μ‐NO site. The [CuIICuIII(μ‐O)(μ‐NO)]2+complex is also competent forO‐nitrosation of MeOH. A rare [CuIICuII(μ‐NO)(OMe)]2+intermediate was isolated and fully characterized, suggesting theS‐nitrosation may proceed through the intermediary of analogous [CuIICuII(μ‐NO)(SR)]2+species. This redox‐ and proton‐neutralS‐nitrosation process is the first functional model of ceruloplasmin in mediatingS‐nitrosation of external thiols, with implications for biological copper sites in the interconversion of NO./RSNO.