由空间位阻NS-硫醚配体支撑的单核、非血红素、高自旋{FeNO}配合物
Mononuclear, Nonheme, High-Spin {FeNO} Complexes Supported by a Sterically Encumbered NS-Thioether Ligand.
作者信息
Confer Alex M, Sabuncu Sinan, Siegler Maxime A, Moënne-Loccoz Pierre, Goldberg David P
机构信息
Department of Chemistry , The Johns Hopkins University , Baltimore , Maryland 21218 , United States.
Department of Biochemistry & Molecular Biology , Oregon Health & Science University , Portland , Oregon 97239 , United States.
出版信息
Inorg Chem. 2019 Aug 5;58(15):9576-9580. doi: 10.1021/acs.inorgchem.9b01475. Epub 2019 Jul 22.
The synthesis of a new nonheme iron NO binding complex, Fe(CHCN)(N3PySEtCN) (), is reported. Complex , which contains two sterically encumbering phenyl substituents, exhibits a high-spin (hs) Fe ( = 2) ground state in contrast to the = 0 ground state for unsubstituted [Fe(CHCN)(N3PySEtCN)(BF). Reaction of with NO in CHCN yields an {FeNO} ( = /) complex , which slowly decays at 25 °C with loss of NO to regenerate . One-electron reduction of with Cr(CH) at -40 °C yields the metastable, = 1 {FeNO} complex . The nitrosyl moieties in thioether-ligated and are significantly less activated than in thiolate-ligated [Fe(NO)(N3PyS)], a structurally analogous pair of hs {FeNO} complexes. Calculations reveal that reduction of is iron-centered, which may be a general property of hs {FeNO} complexes.
报道了一种新的非血红素铁-一氧化氮结合配合物Fe(CHCN)(N3PySEtCN)（）的合成。配合物含有两个空间位阻较大的苯基取代基，与未取代的[Fe(CHCN)(N3PySEtCN)(BF)的基态 = 0 相反，呈现高自旋（hs）铁（ = 2）基态。在 CHCN 中与 NO 反应生成{FeNO}（ = /）配合物，其在 25 °C 下缓慢分解，损失 NO 以再生。在 -40 °C 下用 Cr(CH)对进行单电子还原生成亚稳的 = 1 {FeNO}配合物。硫醚配位的和中的亚硝酰基部分的活性明显低于硫醇盐配位的[Fe(NO)(N3PyS)]，后者是一对结构类似的 hs {FeNO}配合物。计算表明的还原是以铁为中心的，这可能是 hs {FeNO}配合物的普遍性质。
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