Insertion of CO(2) Mediated by a (Xantphos)Ni(I) -Alkyl Species.
Insertion of CO(2) Mediated by a (Xantphos)Ni(I) -Alkyl Species.
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DOI：
10.1002/anie.201906005
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发表时间：
2019-09-23
期刊：
影响因子：
--
通讯作者：
Diao T
中科院分区：
文献类型：
--
作者：
Diccianni JB;Hu CT;Diao T
将二氧化碳掺入有机金属和有机分子中是制备羧酸盐的一种可持续方法。提出了烷基卤化物还原羧化反应的机理，即通过Zn或Mn将NiII还原为NiI，然后在NiI-烷基中插入CO2。之前没有实验证据支持这两个步骤。本文证明了Zn直接还原（tBuXantphos）NiIIBr2得到NiI物种。（tBu-Xantphos）- ni - me和（tBu-Xantphos）NiI-Et配合物在22°C下快速插入CO2。相对于NiII配合物而言，其更快的速率为ni催化羧化反应的机制提供了长期寻求的实验支持。
The incorporation of CO2 into organometallic and organic molecules represents a sustainable way to prepare carboxylates. The mechanism of reductive carboxylation of alkyl halides has been proposed to proceed through the reduction of NiII to NiI by either Zn or Mn, followed by CO2 insertion into NiI-alkyl species. No experimental evidence has been previously established to support the two proposed steps. Demonstrated herein is that the direct reduction of (tBuXantphos)NiIIBr2 by Zn affords NiI species. (tBu-Xantphos)-NiI-Me and (tBu-Xantphos)NiI-Et complexes undergo fast insertion of CO2 at 22°C. The substantially faster rate, relative to that of NiII complexes, serves as the long-sought-after experimental support for the proposed mechanisms of Ni-catalyzed carboxylation reactions.
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