Insights into mechanism and selectivity in ruthenium(II)-catalysed ortho-arylation reactions directed by Lewis basic groups

Jamie McIntyre, Irene Mayoral-Soler, Pedro Salvador Sedano, Albert Poater, David James Nelson

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

We report a detailed study of the selectivity of ruthenium-catalysed C-H arylation reactions directed by Lewis basic heterocycles. A reactivity scale for directing power in these reactions, based on the results of intermolecular competition experiments, is reported for the first time. Our work is supported by detailed density functional theory calculations that reveal the underlying mechanism of this reaction, which requires the dissociation of a p-cymene ligand before oxidative addition becomes competent. The calculated energetic span of the catalytic cycles for each substrate is broadly in agreement with our experimental observations. This work advances our understanding of mechanism and selectivity in these reactions, and provides a basis for future catalyst design efforts.
LanguageEnglish
JournalCatalysis Science and Technology
Early online date1 Jun 2018
DOIs
Publication statusE-pub ahead of print - 1 Jun 2018

Fingerprint

Ruthenium
Density functional theory
Ligands
Catalysts
Substrates
Experiments
4-cymene

Keywords

  • ruthenium-catalysed C-H arylation
  • Lewis basic heterocycles
  • density functional theory calculations
  • catalytic cycles

Cite this

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abstract = "We report a detailed study of the selectivity of ruthenium-catalysed C-H arylation reactions directed by Lewis basic heterocycles. A reactivity scale for directing power in these reactions, based on the results of intermolecular competition experiments, is reported for the first time. Our work is supported by detailed density functional theory calculations that reveal the underlying mechanism of this reaction, which requires the dissociation of a p-cymene ligand before oxidative addition becomes competent. The calculated energetic span of the catalytic cycles for each substrate is broadly in agreement with our experimental observations. This work advances our understanding of mechanism and selectivity in these reactions, and provides a basis for future catalyst design efforts.",
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Insights into mechanism and selectivity in ruthenium(II)-catalysed ortho-arylation reactions directed by Lewis basic groups. / McIntyre, Jamie; Mayoral-Soler, Irene; Salvador Sedano, Pedro; Poater, Albert; Nelson, David James.

In: Catalysis Science and Technology, 01.06.2018.

Research output: Contribution to journalArticle

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T1 - Insights into mechanism and selectivity in ruthenium(II)-catalysed ortho-arylation reactions directed by Lewis basic groups

AU - McIntyre, Jamie

AU - Mayoral-Soler, Irene

AU - Salvador Sedano, Pedro

AU - Poater, Albert

AU - Nelson, David James

PY - 2018/6/1

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N2 - We report a detailed study of the selectivity of ruthenium-catalysed C-H arylation reactions directed by Lewis basic heterocycles. A reactivity scale for directing power in these reactions, based on the results of intermolecular competition experiments, is reported for the first time. Our work is supported by detailed density functional theory calculations that reveal the underlying mechanism of this reaction, which requires the dissociation of a p-cymene ligand before oxidative addition becomes competent. The calculated energetic span of the catalytic cycles for each substrate is broadly in agreement with our experimental observations. This work advances our understanding of mechanism and selectivity in these reactions, and provides a basis for future catalyst design efforts.

AB - We report a detailed study of the selectivity of ruthenium-catalysed C-H arylation reactions directed by Lewis basic heterocycles. A reactivity scale for directing power in these reactions, based on the results of intermolecular competition experiments, is reported for the first time. Our work is supported by detailed density functional theory calculations that reveal the underlying mechanism of this reaction, which requires the dissociation of a p-cymene ligand before oxidative addition becomes competent. The calculated energetic span of the catalytic cycles for each substrate is broadly in agreement with our experimental observations. This work advances our understanding of mechanism and selectivity in these reactions, and provides a basis for future catalyst design efforts.

KW - ruthenium-catalysed C-H arylation

KW - Lewis basic heterocycles

KW - density functional theory calculations

KW - catalytic cycles

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