Dr. Belén Lerma–Berlanga, Dr. Antonio Leyva–Pérez.
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引用次数: 0
摘要
反应分子在金属原子上的氧化加成-还原消除(OARE)机理是现代化学的基石。然而,尽管金属原子和进入的有机反应物之间的第一还原反应在大量过程中具有化学意义,但互补的还原加成-氧化消去(RAOE)机理却很少被考虑。在此,我们按时间顺序展示了文献中表明一般 RAOE 机理可能性的早期先例、迄今为止明确报道的少数体系(包括一个催化体系)以及 RAOE 机理可以令人满意地解释所发现的机理证据的一些其他反应。这些例子强烈建议研究人员在研究过程中考虑 RAOE 机制,而不是简单地将结论调整为普遍存在的 OARE 机制。这种新思路可能会为化学反应(尤其是催化反应)的设计开辟新的途径。
The Reductive Addition–Oxidative Elimination Mechanism
The oxidative addition–reductive elimination (OARE) mechanism of reactive molecules on metal atoms is a cornerstone of modern chemistry. However, the complementary reductive addition–oxidative elimination (RAOE) mechanism is barely considered, despite a first reduction reaction between metal atoms and the incoming organic reactant makes chemical sense in a plethora of processes. Here we show, in a chronological order, early precedents in the literature which indicated the possibility of a general RAOE mechanism, the few systems explicitly reported so far (including a catalytic system) and some other reactions where a RAOE mechanism would satisfactorily explain the mechanistic evidences found. These examples, together, strongly suggest that researchers should consider the RAOE mechanism during their investigations, and not simply adjust their conclusions to the omnipresent OARE mechanism. This new line of thinking might open new avenues in the design of chemical reactions, particularly catalytic ones.