Base Metal Catalysts for Photochemical C-H Borylation That Utilize Metal-Metal Cooperativity
Base Metal Catalysts for Photochemical C-H Borylation That Utilize Metal-Metal Cooperativity
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DOI：
10.1021/ja408861p
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发表时间：
2013-11-20
影响因子：
15
通讯作者：
Mankad, Neal P.
中科院分区：
文献类型：
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作者：
Mazzacano, Thomas J.;Mankad, Neal P.
异双金属 Cu-Fe 和 Zn-Fe 络合物可催化 C-H 硼基化，这是一种以前需要贵金属催化剂的转变。最佳催化剂 (IPr)Cu-FeCp(CO)(2) 在光化学条件下在 5 mol% 负载量下表现出高效活性，重复使用后活性仅略有下降，并且能够催化多种芳烃底物的硼基化。化学计量反应性研究与提出的利用金属-金属协同性的机制一致，并展示了经典有机金属过程、氧化加成和还原消除的双金属版本。
Heterobimetallic Cu-Fe and Zn-Fe complexes catalyze C-H borylation, a transformation that previously required noble metal catalysts. The optimal catalyst, (IPr)Cu-FeCp(CO)(2), exhibits efficient activity at 5 mol% loading under photochemical conditions, shows only minimal decrease in activity upon reuse, and is able to catalyze borylation of a variety of arene substrates. Stoichiometric reactivity studies are consistent with a proposed mechanism that exploits metal-metal cooperativity and showcases bimetallic versions of the classical organometallic processes, oxidative addition and reductive elimination.