Group 9 Metallacyclopentadienes as Key Intermediates in [2+2+2] Alkyne Cyclotrimerizations. Insight from Activation Strain Analyses

Marco Dalla Tiezza, F. Matthias Bickelhaupt*, Laura Orian

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

The intramolecular oxidative coupling converting a bis-acetylene complex of formula CpM (C2H2)2 (Cp=C5H5 ; M=Co, Rh, Ir) into a 16-electron metallacycle is studied in silico. This reaction is paradigmatic in acetylene [2+2+2] cycloaddition to benzene catalyzed by CpM fragments, being the step with the highest activation energy, and thus affecting the whole catalysis. Our activation strain and quantitative molecular orbital (MO) analyses elucidate the mechanistic details and reveal why cobalt performs better than rhodium and iridium catalysts outlining general principles for rational design of catalysts to be used in these processes.

Original languageEnglish
Pages (from-to)1766-1773
Number of pages8
JournalChemPhysChem
Volume19
Issue number14
Early online date10 Apr 2018
DOIs
Publication statusPublished - 17 Jul 2018

Keywords

  • activation-strain analysis
  • group 9 metals
  • metallacyclopentadienes
  • oxidative coupling
  • reaction mechanism

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