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Neutral Ni(II) Catalysts Based on Maple-Lactone Derived [N,O] Ligands for the Polymerization of Ethylene
Organometallics ( IF 2.5 ) Pub Date : 2020-04-17 , DOI: 10.1021/acs.organomet.0c00061 Matthew J. Andrews 1 , Paul M. D. A. Ewing 1 , Martyn C. Henry 1 , Mark Reeves 1 , Paul C. J. Kamer 2 , Bernd H. Müller 2 , Ruaraidh D. McIntosh 1 , Stephen M. Mansell 1
Organometallics ( IF 2.5 ) Pub Date : 2020-04-17 , DOI: 10.1021/acs.organomet.0c00061 Matthew J. Andrews 1 , Paul M. D. A. Ewing 1 , Martyn C. Henry 1 , Mark Reeves 1 , Paul C. J. Kamer 2 , Bernd H. Müller 2 , Ruaraidh D. McIntosh 1 , Stephen M. Mansell 1
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This paper describes the synthesis of neutral nickel(II) catalysts for the polymerization of ethylene. A series of 2-(arylamino)-5-methylcyclopent-2-en-1-one (aryl = 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl, 3,5-dimethylphenyl, and 4-methylphenyl) proligands, derived from the condensation of aryl amines with maple lactone, were synthesized as their keto-enamine tautomers. Deprotonation with NaH gave their respective sodium imino-enolate salts, which underwent salt metathesis with Ni(II) precursors to give square planar [Ni(Ar)(κ2-imino-enolate)(PPh3)] (Ar = Ph, ortho-tolyl) complexes containing 5-membered [N,O] chelates. Precatalysts with N-Dipp (Dipp = 2,6-diisopropylphenyl) substituents were found to exhibit moderate activity in the polymerization of ethylene when using B(C6F5)3 or [Ni(cod)2] (cod = 1,4-cyclooctadiene) as coactivators, producing polymers with a high molecular weight, as determined by GPC. The reaction was found to be highly dependent on temperature, with the catalysts most active at 80 °C. Differences in polymer structure were also found when using B(C6F5)3 or [Ni(cod)2] as the cocatalyst, with [Ni(cod)2] producing a more highly branched polymer. Reducing the steric bulk at the N substituent of the ligand led to inactive species.
中文翻译：
基于槭内酯[N，O]配体的中性Ni（II）催化剂用于乙烯聚合
本文介绍了用于乙烯聚合的中性镍（II）催化剂的合成。一系列2-（芳基氨基）-5-甲基环戊-2-烯-1-酮（芳基= 2,6-二异丙基苯基，2,4,6-三甲基苯基，3,5-二甲基苯基和4-甲基苯基）配体，衍生自芳基胺与枫酸内酯缩合得到的酮-烯胺互变异构体。去质子化用NaH，得到它们各自的钠亚氨基烯醇盐，其盐后行复分解用Ni（II）的前体，得到正方形平面[镍（AR）（κ 2 -亚氨基-烯醇化物）（PPH 3）]（Ar为PH，邻-tolyl）配合物，含有5元[N，O]螯合物。当使用B（C 6 F 5）3或[Ni（cod）2 ]（cod = 1,4 ）时，发现具有N-Dipp（Dipp = 2,6-二异丙基苯基）取代基的预催化剂在乙烯的聚合反应中显示中等活性。-环辛二烯）作为助活化剂，可生产出具有高分子量的聚合物（通过GPC测定）。发现该反应高度依赖于温度，催化剂在80℃下最具活性。当使用B（C 6 F 5）3或[Ni（cod）2 ]作为助催化剂和[Ni（cod）2时，也发现聚合物结构存在差异。产生更高支化的聚合物。减少配体的N取代基上的空间体积导致无活性物质。
更新日期：2020-04-17
中文翻译：
基于槭内酯[N，O]配体的中性Ni（II）催化剂用于乙烯聚合
本文介绍了用于乙烯聚合的中性镍（II）催化剂的合成。一系列2-（芳基氨基）-5-甲基环戊-2-烯-1-酮（芳基= 2,6-二异丙基苯基，2,4,6-三甲基苯基，3,5-二甲基苯基和4-甲基苯基）配体，衍生自芳基胺与枫酸内酯缩合得到的酮-烯胺互变异构体。去质子化用NaH，得到它们各自的钠亚氨基烯醇盐，其盐后行复分解用Ni（II）的前体，得到正方形平面[镍（AR）（κ 2 -亚氨基-烯醇化物）（PPH 3）]（Ar为PH，邻-tolyl）配合物，含有5元[N，O]螯合物。当使用B（C 6 F 5）3或[Ni（cod）2 ]（cod = 1,4 ）时，发现具有N-Dipp（Dipp = 2,6-二异丙基苯基）取代基的预催化剂在乙烯的聚合反应中显示中等活性。-环辛二烯）作为助活化剂，可生产出具有高分子量的聚合物（通过GPC测定）。发现该反应高度依赖于温度，催化剂在80℃下最具活性。当使用B（C 6 F 5）3或[Ni（cod）2 ]作为助催化剂和[Ni（cod）2时，也发现聚合物结构存在差异。产生更高支化的聚合物。减少配体的N取代基上的空间体积导致无活性物质。
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