Insertion of CO 2 Mediated by a (Xantphos)Ni I -Alkyl Species

The incorporation of CO 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 Ni to Ni by either Zn or Mn, followed by CO insertion into Ni -alkyl...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2019-09, Vol.58 (39), p.13865-13868
Main Authors: Diccianni, Justin B, Hu, Chunhua T, Diao, Tianning
Format: Article
Language:English
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Summary:The incorporation of CO 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 Ni to Ni by either Zn or Mn, followed by CO insertion into Ni -alkyl species. No experimental evidence has been previously established to support the two proposed steps. Demonstrated herein is that the direct reduction of (tBu-Xantphos)Ni Br by Zn affords Ni species. (tBu-Xantphos)Ni -Me and (tBu-Xantphos)Ni -Et complexes undergo fast insertion of CO at 22 °C. The substantially faster rate, relative to that of Ni complexes, serves as the long-sought-after experimental support for the proposed mechanisms of Ni-catalyzed carboxylation reactions.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201906005