Catalytic Synthesis of a Methylmalonate Salt from Ethylene and Carbon Dioxide through Photoinduced Activation and Photoredox-Catalyzed Reduction of Nickelalactones
Catalytic Synthesis of a Methylmalonate Salt from Ethylene and Carbon Dioxide through Photoinduced Activation and Photoredox-Catalyzed Reduction of Nickelalactones
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DOI：
10.1021/acscatal.2c01053
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发表时间：
2022-03
期刊：
影响因子：
12.9
通讯作者：
Kohei Takahashi;Yuji Sakurazawa;Asaki Iwai;N. Iwasawa
中科院分区：
文献类型：
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作者：
Kohei Takahashi;Yuji Sakurazawa;Asaki Iwai;N. Iwasawa
采用Ni/Ir双催化剂体系，在光照条件下催化乙烯与CO2发生1，1-二羧基化反应生成丙二酸甲酯。在该反应中，光能不仅用于还原甲基丙二酸镍（II）络合物，而且用于镍内酯转化为甲基丙二酸络合物。通过仔细的机理研究，它被揭示，光照射不仅促进五元到四元镍内酯的异构化，但也插入的第二个分子的CO2形成甲基丙二酸配合物通过三重态激发态的四元镍内酯。这是由乙烯和CO2催化合成丙二酸甲酯的一个前所未有的例子。
Catalytic 1,1-dicarboxylation of ethylene with CO2to form a methylmalonate salt was achieved by a Ni/Ir dual-catalyst system under photoirradiation conditions. In this reaction, photoenergy was utilized not only for the reduction of the methylmalonate Ni(II) complex but also for the transformation of the nickelalactone to the methylmalonate complex. By careful mechanistic investigations, it was revealed that photoirradiation promotes not only isomerization of five-membered to four-membered nickelalactones but also insertion of the second molecule of CO2to form methylmalonate complexes via triplet excited states of the four-membered nickelalactones. This is an unprecedented example of catalytic methylmalonate synthesis from ethylene and CO2.