Preparation and characterization of the triflate complex [Cp*(dppe)Fe-OSO2CF3]: a convenient access to labile five- and six-coordinate Fe(I) and Fe(II) complexes,European Journal of Inorganic Chemistry

当前位置： X-MOL 学术 › Eur. J. Inorg. Chem. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Preparation and characterization of the triflate complex [Cp*(dppe)Fe-OSO2CF3]: a convenient access to labile five- and six-coordinate Fe(I) and Fe(II) complexes
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2019-12-03 , DOI: 10.1002/ejic.201901086
Paul Hamon ₁ , Loic Toupet ₂ , Thierry Roisnel ₁ , Jean-René Hamon ₁ , Claude Lapinte ₁

Affiliation

Treatment of the iron hydride [Cp*(dppe)FeH] (1) with methyl triflate (CH3OSO2CF3) yielded the iron triflate adduct [Cp*(dppe)FeOSO2CF3] (4, 85 %). In the solid state, the triflate is coordinated at the iron center as shown by XRD (d(Fe-O) = 2.118(4) angstrom) and IR spectroscopy (nu(SO) = 1305 cm(-1)). In solution, 4 is in equilibrium with the 16-electron species [Cp*(dppe)Fe]OSO2CF3 (5(OSO2CF3)), 4/5(OSO2CF3) = 21). The CV of 4 displays two waves (E-1 = -0.74 V, E-2 = 0.24 V vs. SCE) assigned to the [Cp*(dppe)Fe(I)]/[Cp*(dppe)Fe(II)](+) and [Cp*(dppe)Fe(II)](+)/[Cp*(dppe)Fe(III)](2+) redox couples. Reduction of 4 with Cp2Co provided the complex [Cp*(dppe)Fe(I)] (6, 95 %) and oxidation of 6 with [Cp2Fe]PF6 gave [Cp*(dppe)Fe]PF6 (5(PF6), 98 %). XRD established the pseudo-trigonal bipyramidal geometry for the five-coordinated cation 5(+). The reactivity of 5(PF6) and 6 toward small molecules (CH2Cl2, H2O, CO, H-2, N-2) is reported.

中文翻译：

三氟甲磺酸盐配合物 [Cp*(dppe)Fe-OSO2CF3] 的制备和表征：方便获得不稳定的五和六配位 Fe(I) 和 Fe(II) 配合物

用三氟甲磺酸甲酯 (CH3OSO2CF3) 处理氢化铁 [Cp*(dppe)FeH] (1) 产生三氟甲磺酸铁加合物 [Cp*(dppe)FeOSO2CF3] (4, 85%)。在固态下，三氟甲磺酸盐在铁中心配位，如 XRD (d(Fe-O) = 2.118(4) 埃) 和红外光谱 (nu(SO) = 1305 cm(-1)) 所示。在溶液中，4 与 16 种电子 [Cp*(dppe)Fe]OSO2CF3 (5(OSO2CF3))、4/5(OSO2CF3) = 21 处于平衡状态。4 的 CV 显示分配给 [Cp*(dppe)Fe(I)]/[Cp*(dppe)Fe(II) 的两个波（E-1 = -0.74 V，E-2 = 0.24 V vs. SCE） )](+) 和 [Cp*(dppe)Fe(II)](+)/[Cp*(dppe)Fe(III)](2+) 氧化还原对。用 Cp2Co 还原 4 提供复合物 [Cp*(dppe)Fe(I)] (6, 95 %)，用 [Cp2Fe]PF6 氧化 6 得到 [Cp*(dppe)Fe]PF6 (5(PF6)， 98%）。XRD 为五配位阳离子 5(+) 建立了伪三角双锥几何结构。

更新日期：2019-12-03

点击分享查看原文

点击收藏

公开下载

阅读更多本刊新发论文本刊介绍/投稿指南