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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >(Phenoxyimidazolyl-salicylaldimine)iron complexes: synthesis, properties and iron catalysed ethylene reactions
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(Phenoxyimidazolyl-salicylaldimine)iron complexes: synthesis, properties and iron catalysed ethylene reactions

机译：（苯氧基咪唑基-水杨醛亚胺）铁配合物：合成，性质和铁催化的乙烯反应

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The reaction of 2-{[2-(1H-imidazol-4-yl)-ethylimino]-methyl}-phenol (L1), 2,4-di-tert-butyl-6-{[2-(1Himidazol- 4-yl)-ethylimino]-methyl}-phenol (L2) or 4-tert-butyl-2-{[2-(1H-imidazol-4-yl)-ethylimino]- methyl}-phenol (L3) with iron(II) precursors produced either iron(II) or iron(III) complexes, depending on the nature of the anions in the iron(II) precursor and the ligand. When the anion is chloride and the ligand L1, the product is [(L1)_2Fe][FeCl_4] (1), but when the anion is triflate (OTf~?) and the ligand is L2, the product is [(L2)_2Fe][OTf]_2 (2). With iron(II) halides and tert-butyl groups on the phenoxy ligands L2 and L3, the iron(III) complexes [(L2)FeX_2] {where X = Cl (3), Br (4) and I = (5)} and [(L3)FeCl_2] (6) were formed. Complexes 1–6 were characterised by a combination of elemental analyses, IR spectroscopy and mass spectrometry; and in selected cases (3 and 4) by single crystal X-ray crystallography. The crystal structures of 3 and 4 indicated that the iron(II) precursors oxidised to iron(III) in forming complexes 3–6; an observation that was corroborated by the magnetic properties and the ~(57)Fe M?ssbauer spectra of 3 and 4. The iron(III) complexes 3–6 were used as pre-catalysts for the oligomerisation and polymerisation of ethylene. Products of these ethylene reactions depended on the solvent used. In toluene ethylene oligomerised mainly to 1-butene and was followed by the 1-butene alkylating the solvent to form butyl-toluenes via a Friedel–Crafts alkylation reaction. In chlorobenzene, ethylene oligomerised mainly to a mixture of C_4–C_(12) alkenes. Interestingly small amounts of butyl-chlorobenzenes and hexyl-chlorobenzenes were also formed via a Friedel–Crafts alkylation with butenes and hexenes from the oligomerisation of ethylene.
机译：2-{[2-（1H-咪唑-4-基）-乙基亚氨基]-甲基}-苯酚（L1），2,4-二叔丁基-6-{[2-（1Himidazol-4 -基）-乙基亚氨基]-甲基}-苯酚（L2）或4-叔丁基-2-{[2-（1H-咪唑-4-基）-乙基亚氨基]-甲基}-苯酚（L3）与铁（ II）前体产生铁（II）或铁（III）络合物，具体取决于铁（II）前体和配体中阴离子的性质。当阴离子为氯离子且配体为L1时，乘积为[（L1）_2Fe] [FeCl_4]（1）;而当阴离子为三氟甲磺酸根（OTf〜？）且配体为L2时，乘积为[（L2） _2Fe] [OTf] _2（2）。苯氧基配体L2和L3上具有卤化铁（II）和叔丁基，这些铁（III）络合物[（L2）FeX_2] {其中X = Cl（3），Br（4）和I =（5） }和[（L3）FeCl_2]（6）形成。配合物1-6的特征在于结合了元素分析，红外光谱和质谱。在某些情况下（3和4）通过单晶X射线晶体学。 3和4的晶体结构表明，铁（II）的前体在形成配合物3-6时被氧化为铁（III）。 3和4的磁性和〜（57）Fe M？ssbauer光谱证实了这一观察结果。铁（III）配合物3-6被用作乙烯低聚和聚合的预催化剂。这些乙烯反应的产物取决于所用溶剂。在甲苯中，乙烯主要低聚为1-丁烯，然后通过Friedel-Crafts烷基化反应将1-丁烯烷基化以形成丁基甲苯。在氯苯中，乙烯主要低聚为C4-C_（12）烯烃的混合物。有趣的是，少量的丁基-氯苯和己基-氯苯还通过与乙烯的低聚反应得到的丁烯和己烯的弗瑞德-克来福特烷基化反应形成。

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