Francis K. Migwi, George S. Nyamato, Stephen O. Ojwach
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These new complexes are characterized using fourier transform-infra red and ultra-violet (UV)–Visible spectroscopies, elemental analysis, and single crystal X-ray crystallography diffraction for complexes <b>Co2</b> and <b>Co3</b>. The molecular structures of <b>Co2</b> and <b>Co3</b> confirm the formation of the dinuclear cobalt species. Activation of the precatalysts <b>Co1</b>–<b>Co4</b> with either EtAlCl<sub>2</sub> or Me<sub>3</sub>Al, affords active (up to 5.26 × 10<sup>5</sup> g·mol<sup>−1</sup>Co h<sup>−1</sup>) and selective ethylene dimerization (>98%) catalysts. The steric parameters of the coordinated ligands, as dictated by the substituents on the pyrazolyl ring, largely controll both the activity and regioselectivity of the resultant catalysts.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 22","pages":""},"PeriodicalIF":2.0000,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500204","citationCount":"0","resultStr":"{\"title\":\"Dinuclear Benzene Linker Bis(pyrazolyl)amine Cobalt(II) Complexes and their Application as Selective Ethylene Dimerization Catalysts\",\"authors\":\"Francis K. Migwi, George S. Nyamato, Stephen O. Ojwach\",\"doi\":\"10.1002/ejic.202500204\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Reactions of synthons <i>N</i>,<i>N′</i>-(1,4-phenylenebis(methylene))bis(2-(1<i> H</i>-pyrazol-1-yl)ethan-1-amine) (<b>L1)</b>, <i>N</i>,<i>N</i>′-(1,4-phenylenebis(methylene))bis(2-(3,5-dimethyl-1<i> H</i>-pyrazol-1-yl)ethan-1-amine) (<b>L2)</b>, <i>N</i>,<i>N</i>′-(1,4-phenylenebis(methylene))bis(2-(3,5-di-<i>tert</i>-butyl-1<i> H</i>-pyrazol-1-yl)ethan-1-amine) (<b>L3)</b>, and <i>N</i>,<i>N</i>′-(1,3-phenylenebis(methylene))bis(2-(3,5-dimethyl-1<i> H</i>-pyrazol-1-yl)ethan-1-amine) (<b>L4)</b> with CoCl<sub>2</sub> produce the dinuclear cobalt(II) complexes [Co<sub>2</sub>(<b>L1</b>)Cl<sub>4</sub>] (<b>Co1</b>), [Co<sub>2</sub>(<b>L2</b>)Cl<sub>4</sub>] (<b>Co2</b>), [Co<sub>2</sub>(<b>L3</b>)Cl<sub>4</sub>] (<b>Co3</b>), and [Co<sub>2</sub>(<b>L4</b>)Cl<sub>4</sub>] (<b>Co4</b>), respectively. 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引用次数: 0
摘要
反应合成纤维的N, N ' - (1, 4-phenylenebis(亚甲基)二(2 - (1 H-pyrazol-1-yl) ethan-1-amine) (L1), N, N ' - (1, 4-phenylenebis(亚甲基)二(2 - (3,5-dimethyl-1 H-pyrazol-1-yl) ethan-1-amine) (L2), N, N ' - (1, 4-phenylenebis(亚甲基)二(2 - (3,5-di-tert-butyl-1 H-pyrazol-1-yl) ethan-1-amine) (L3)和N, N ' - (1, 3-phenylenebis(亚甲基)二(2 - (3,5-dimethyl-1 H-pyrazol-1-yl) ethan-1-amine) (L4) CoCl2产生双核的钴(II)配合物(二氧化碳(L1) Cl4] (Co1), (L2) Cl4][二氧化碳(Co2),(二氧化碳(L3) Cl4](二氧化碳),和[Co2(L4)Cl4] (Co4)。利用傅里叶变换-红外和紫外-可见光谱、元素分析和单晶x射线衍射对这些新的配合物Co2和Co3进行了表征。Co2和Co3的分子结构证实了双核钴的形成。用EtAlCl2或Me3Al活化预催化剂Co1-Co4,可获得活性(高达5.26 × 105 g·mol−1Co h−1)和选择性乙烯二聚(98%)催化剂。配位体的空间参数由吡唑基环上的取代基决定,在很大程度上控制了所合成催化剂的活性和区域选择性。
Dinuclear Benzene Linker Bis(pyrazolyl)amine Cobalt(II) Complexes and their Application as Selective Ethylene Dimerization Catalysts
Reactions of synthons N,N′-(1,4-phenylenebis(methylene))bis(2-(1 H-pyrazol-1-yl)ethan-1-amine) (L1), N,N′-(1,4-phenylenebis(methylene))bis(2-(3,5-dimethyl-1 H-pyrazol-1-yl)ethan-1-amine) (L2), N,N′-(1,4-phenylenebis(methylene))bis(2-(3,5-di-tert-butyl-1 H-pyrazol-1-yl)ethan-1-amine) (L3), and N,N′-(1,3-phenylenebis(methylene))bis(2-(3,5-dimethyl-1 H-pyrazol-1-yl)ethan-1-amine) (L4) with CoCl2 produce the dinuclear cobalt(II) complexes [Co2(L1)Cl4] (Co1), [Co2(L2)Cl4] (Co2), [Co2(L3)Cl4] (Co3), and [Co2(L4)Cl4] (Co4), respectively. These new complexes are characterized using fourier transform-infra red and ultra-violet (UV)–Visible spectroscopies, elemental analysis, and single crystal X-ray crystallography diffraction for complexes Co2 and Co3. The molecular structures of Co2 and Co3 confirm the formation of the dinuclear cobalt species. Activation of the precatalysts Co1–Co4 with either EtAlCl2 or Me3Al, affords active (up to 5.26 × 105 g·mol−1Co h−1) and selective ethylene dimerization (>98%) catalysts. The steric parameters of the coordinated ligands, as dictated by the substituents on the pyrazolyl ring, largely controll both the activity and regioselectivity of the resultant catalysts.
期刊介绍:
The European Journal of Inorganic Chemistry (2019 ISI Impact Factor: 2.529) publishes Full Papers, Communications, and Minireviews from the entire spectrum of inorganic, organometallic, bioinorganic, and solid-state chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies.
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