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

doi:10.1002/cphc.201800178

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 Journal › Article › Academic › peer-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 language	English
Pages (from-to)	1766-1773
Number of pages	8
Journal	ChemPhysChem
Volume	19
Issue number	14
Early online date	10 Apr 2018
DOIs	https://doi.org/10.1002/cphc.201800178
Publication status	Published - 17 Jul 2018

Keywords

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

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

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.",

keywords = "activation-strain analysis, group 9 metals, metallacyclopentadienes, oxidative coupling, reaction mechanism",

author = "{Dalla Tiezza}, Marco and Bickelhaupt, {F. Matthias} and Laura Orian",

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AU - Bickelhaupt, F. Matthias

AU - Orian, Laura

PY - 2018/7/17

Y1 - 2018/7/17

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AB - 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.

KW - activation-strain analysis

KW - group 9 metals

KW - metallacyclopentadienes

KW - oxidative coupling

KW - reaction mechanism

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

Abstract

Keywords

UN SDGs

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