Cyclotrimerization

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Matthias F Bickelhaupt - One of the best experts on this subject based on the ideXlab platform.

  • indenyl effect due to metal slippage computational exploration of rhodium catalyzed acetylene 2 2 2 Cyclotrimerization
    ChemPhysChem, 2014
    Co-Authors: Laura Orian, Marcel Swart, Matthias F Bickelhaupt
    Abstract:

    The mechanism of CpRh (Cp=cyclopentadienyl) and IndRh (Ind=indenyl)-catalyzed acetylene [2+2+2] Cyclotrimerization has been revisited aiming at finding an explanation for the better performance of the latter catalyst found experimentally. The hypothesis that an ancillary ligand of the precatalyst remains bonded to the metal center throughout the whole catalytic cycle, based on the experimental evidence that the nature of this ligand can exert some control in coCyclotrimerization of different alkynes, is considered. Strong hapticity variations occur in both the CpRh- and IndRh-catalyzed processes. As the Ind ligand undergoes a more facile slippage than Cp, the energy profile is far smoother in the IndRh-catalyzed Cyclotrimerization. This difference in the energetics of the process translates into an enhanced activity of the IndRh catalyst, in nice agreement with experiment.

Martin Kotora - One of the best experts on this subject based on the ideXlab platform.

Gaddamedi Sreevani - One of the best experts on this subject based on the ideXlab platform.

Alexander Deiters - One of the best experts on this subject based on the ideXlab platform.

Chepuri V. Ramana - One of the best experts on this subject based on the ideXlab platform.