The utilization of renewable carbon dioxide resources in the production of commercial chemicals has been at the center of efforts to improve the sustainability of many widely used consumer products. The catalytic coupling of CO₂ with ethylene to generate acrylates is one such avenue of research. Despite decades of investigations, catalytic CO₂–ethylene coupling has only recently been experimentally demonstrated. The development of a new nickel-based catalyst, 1,2-bis(di-iso-propylphosphino)benzene nickel(0) 1,5-cyclooctadiene, for acrylate production is detailed here. The stoichiometric reactivity of the catalyst toward the CO₂, ethylene, and base reagents, as well as the coordination chemistry of likely catalytic intermediates has been examined. Comparative catalytic experiments were used to identify the influence of commonly employed additives, such as metallic zinc and Lewis acidic salts, on the catalytic CO₂–ethylene coupling reaction. In addition, catalytic comparisons of the 1,2-bis(di-iso-propylphosphino)benzene nickel(0) 1,5-cyclooctadiene species with a similar previously reported catalyst under newly developed conditions afforded turnover numbers greater than 400, an approximately 4-fold increase over the highest activity reported to date. Significantly, the catalytic trials reveal that small changes in the catalytic conditions and additives can have substantial effects on productivity and that these influences are not uniform with respect to catalyst platforms.

中文翻译：

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合成和1,2-双的反应活性（二-异-propylphosphino）苯镍配合：催化CO的研究₂ -乙烯耦合

在商业化学品生产中利用可再生二氧化碳资源一直是提高许多广泛使用的消费品可持续性的努力中心。这样的研究途径之一就是CO ₂与乙烯的催化偶合以生成丙烯酸酯。尽管进行了数十年的研究，但最近才通过实验证明了催化性CO _2-乙烯偶联。一种新的镍基催化剂的发展，1,2-二（二-异-propylphosphino）苯镍（0）1,5-环辛二烯，用于生产丙烯酸酯在此处详细描述。催化剂对CO ₂的化学计量反应性，乙烯和碱试剂，以及可能的催化中间体的配位化学都已经过检查。通过比较催化实验确定了常用的添加剂（例如金属锌和路易斯酸性盐）对催化CO _2-乙烯偶联反应的影响。此外，对1,2-双（二异氰酸酯）进行催化比较-丙基膦基）苯镍（0）1,5-环辛二烯物种与类似的先前报道的催化剂在新开发的条件下提供的周转数大于400，比迄今报道的最高活性高约4倍。重要的是，催化试验表明，催化条件和添加剂的细微变化可对生产率产生实质性影响，并且这些影响相对于催化剂平台而言是不均匀的。