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Indenyl Effect Due to Metal Slippage? Computational Exploration of Rhodium‐Catalyzed Acetylene [2+2+2] Cyclotrimerization
Author(s) -
Orian Laura,
Swart Marcel,
Bickelhaupt F. Matthias
Publication year - 2014
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201300934
Subject(s) - rhodium , acetylene , slippage , metal , catalysis , chemistry , photochemistry , materials science , organic chemistry , composite material
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.