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首页> 外文期刊>Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics >Monomeric bis(anilido)iron(II) complexes with N-heterocyclic carbene ligation: Synthesis, characterization, and redox reactivity toward aryl halides
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Monomeric bis(anilido)iron(II) complexes with N-heterocyclic carbene ligation: Synthesis, characterization, and redox reactivity toward aryl halides

机译：N-杂环卡宾连接的单体双（苯胺基）铁（II）配合物：对芳基卤化物的合成，表征和氧化还原反应性

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摘要

Using monodentate N-heterocyclic carbenes as the ancillary ligands, seven monomeric bis(anilido)iron(II) complexes [(IPr_2Me_2) _2Fe(NHAr)_2] (IPr_2Me_2 = 2,5-diisopropyl-3,4-dimethylimidazol-1-ylidene; Ar = Ph, C_6H _4-2-Pr~i, Mes, C_6H_3-2,6-Cl _2, Dipp) and [(IPr)Fe(NHAr)_2] (IPr = 2,5-di(2,6- diisopropylphenyl)imidazol-1-ylidene; Ar = C_6H_3-2,6- Cl_2, Dipp) have been prepared by the one-pot reactions of [Fe(Mes)_2]_2 with the corresponding N-heterocyclic carbenes, and anilines. These high-spin diamido complexes have been fully characterized by ~1H NMR, solution magnetic susceptibility, UV-vis, IR, X-ray diffraction, cyclic voltammetry, as well as elemental analysis. The strong affinity of the N-heterocyclic carbene ligands toward ferrous centers, and the steric protection exerted by the NHC ligands are the key factors to stabilize these bis(anilido)iron complexes in a monomeric manner. Reactivity studies revealed the four-coordinate complex [(IPr_2Me _2)_2Fe(NHMes)_2] can react with 1 equiv of 1-iodo-3,5-dimethylbenzene or 1-bromo-3,5-dimethylbenzene in C_6D _6 and THF-d_8 to furnish 1-C_6D _5-3,5-Me_2C_6H_3, and 5-D-1,3-Me _2C_6H_3, respectively. Under similar conditions, the three-coordinate compound [(IPr)Fe(NHDipp)_2] is inert toward these halides.
机译：使用单齿N-杂环卡宾作为辅助配体，七个单体双（苯胺基）铁（II）配合物[（IPr_2Me_2）_2Fe（NHAr）_2]（IPr_2Me_2 = 2,5-二异丙基-3,4-二甲基咪唑-1-基; Ar = Ph，C_6H _4-2-Pr〜i，Mes，C_6H_3-2,6-Cl _2，Dipp）和[（IPr）Fe（NHAr）_2]（IPr = 2,5-di（2,6 -通过[Fe（Mes）_2] _2与相应的N-杂环卡宾和苯胺的一锅反应制备了二异丙基苯基）咪唑-1-基亚烷基; Ar ＝ C_6H_3-2,6-Cl_2，Dipp）。这些高自旋二酰胺配合物已通过〜1 H NMR，溶液磁化率，UV-vis，IR，X射线衍射，循环伏安法以及元素分析得到了充分表征。 N-杂环卡宾配体对亚铁中心的强亲和力以及NHC配体所发挥的空间保护作用是以单体方式稳定这些双（苯胺基）铁配合物的关键因素。反应性研究表明，四配位络合物[（IPr_2Me _2）_2Fe（NHMes）_2]可以与1当量的1-碘-3,5-二甲苯或1-溴-3,5-二甲苯在C_6D _6和THF-中反应d_8分别提供1-C_6D _5-3,5-Me_2C_6H_3和5-D-1,3-Me _2C_6H_3。在类似条件下，三配位化合物[（IPr）Fe（NHDipp）_2]对这些卤化物呈惰性。

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