Journal of Organometallic Chemistry ( IF 2.3 ) Pub Date : 2020-07-25 , DOI: 10.1016/j.jorganchem.2020.121436 Wakano Taniguchi , Jun-ichi Ito , Makoto Yamashita
This work studied preparation and catalytic application of CNC-pincer Fe complexes containing a bis(NHC)amido ligand (NHC: N-heterocyclic carbene). Deprotonation of bis(3-isopropylimidazoliumyl)amine salt [(CNCiPr)H3]2+[I−]2 (1a) with lithium hexamethyldisilazide (LiHMDS) afforded the corresponding bis(NHC)amido-Li complex 2a. Treatment of in-situ generated 2a with FeI2(thf)2 gave a CNC-pincer Fe(II) iodide complex Fe(CNCiPr)I (3a) and a cationic homoleptic Fe(III) complex [Fe(CNCiPr)2]+I− (4a). Reaction of in-situ generated 2a with Fe[N(SiMe3)2]2 produced the corresponding amido complex Fe(CNCiPr)[N(SiMe3)2] (5a). Similarly, deprotonation of a less hindered methyl analogue [(CNCMe)H3]2+[I−]2 (1b) with LiHMDS followed by treatment of Fe[N(SiMe3)2]2 gave an amido complex Fe(CNCMe)[N(SiMe3)2] (5b). Molecular structures of 3a, 5a and 5b, which were confirmed by X-ray diffraction study, showed a distorted tetrahedral geometry. Complexes 3a and 5b were found to be active in hydrogenation of alkenes. Reaction mechanism was investigated by density functional theory (DFT) calculations.
中文翻译：
含双（N-杂环卡宾）酰胺基配体的CNC钳制铁络合物：烯烃的合成及其在催化加氢中的应用
这项工作研究了含有双（NHC）酰胺基配体（NHC：N-杂环卡宾）的CNC-钳制Fe络合物的制备和催化应用。双去质子化（3- isopropylimidazoliumyl）胺盐[（CNC我镨）H 3 ] 2+ [I - ] 2（1A）与六甲基二锂，得到相应的双（NHC）酰氨基- Li络合物（将LiHMDS）2A。用FeI 2（thf）2处理原位生成的2a得到CNC钳制的Fe（II）碘化物络合物Fe（CNC i Pr）I（3a）和阳离子均配型的Fe（III）络合物的[Fe（CNC我镨）2 ] +我- （4A）。的反应原位生成的图2a为Fe [N（森达3）2 ] 2产生的对应的酰胺络合物的Fe（CNC我镨）[N（森达3）2 ]（图5a）。类似地，较少受阻甲基类似物的去质子化[（CNC我）H 3 ] 2 + [I - ] 2（1B），然后用LiHMDS处理Fe [N（SiMe 3）2 ] 2，得到酰胺配合物Fe（CNC Me）[N（SiMe 3）2 ]（5b）。X射线衍射研究证实了3a，5a和5b的分子结构显示出扭曲的四面体几何形状。发现络合物3a和5b在烯烃的氢化中具有活性。通过密度泛函理论（DFT）计算研究了反应机理。
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