960205-81-6Relevant academic research and scientific papers
Insertion of CO2 Mediated by a (Xantphos)NiI–Alkyl Species
Diccianni, Justin B.,Hu, Chunhua T.,Diao, Tianning
, p. 13865 - 13868 (2019)
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 (tBu-Xantphos)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.
Synthesis, X-ray, and electronic structures of a new nickel dibromide complex. Activity in the regioselective catalyzed dimerization of ethylene into 1-butene
Mora, Guilhem,Van Zutphen, Steven,Klemps, Christian,Ricard, Louis,Jean, Yves,Le Floch, Pascal
, p. 10365 - 10371 (2008/10/09)
Reaction of the bis-(3,4)-dimethylphosphole-Xanthene 1b with [NiBr 2(DME)] afforded a new nickel(II) dibromide complex, 2. Both its color and its NMR behavior change with temperature and solvent due to changes in the spin state of the complex. This led us to study the complex spin states using DFT calculations. Furthermore, the activity of 2 in catalyzed ethylene dimerization was studied, revealing both high activity and selectivity toward the production of 1-butene.
