Insertion of CO₂ Mediated by a (Xantphos)Ni^I -Alkyl Species

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 Ni^II to Ni^I by either Zn or Mn, followed by CO₂ insertion into Ni^I -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^II Br₂ by Zn affords Ni^I species. (tBu-Xantphos)Ni^I -Me and (tBu-Xantphos)Ni^I -Et complexes undergo fast insertion of CO₂ at 22 °C. The substantially faster rate, relative to that of Ni^II complexes, serves as the long-sought-after experimental support for the proposed mechanisms of Ni-catalyzed carboxylation reactions.