Aromaticity in catalysis: metal ligand cooperation via ligand dearomatization and rearomatization

Unlike the conventional model of transition metal catalysis, ligands in metal–ligand cooperative (or bifunctional) catalysis are involved in the substrate activations. Such processes have offered unique mechanistic understandings and led to new concepts for the catalyst design. In particular, unprec...

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Published inChemical communications (Cambridge, England) Vol. 57; no. 25; pp. 3070 - 3082
Main Authors Gonçalves, Théo P., Dutta, Indranil, Huang, Kuo-Wei
Format Journal Article
LanguageEnglish
Published England Royal Society of Chemistry 28.03.2021
Subjects
Aromaticity
aromatization
Catalysis
catalysts
catalytic activity
Ligands
Substrates
thermodynamics
Transition metals
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Summary:Unlike the conventional model of transition metal catalysis, ligands in metal–ligand cooperative (or bifunctional) catalysis are involved in the substrate activations. Such processes have offered unique mechanistic understandings and led to new concepts for the catalyst design. In particular, unprecedented activities were discovered when the ligand could undergo dearomatization–rearomatization reactions during the catalytic cycle. Aromatization can provide an extra driving force to thermodynamics; consequently, it brings a new perspective to ligand platform design for catalysis. While numerous applications were demonstrated, the influences of changing ligand aromatic properties were often overlooked. In this article, representative ligand systems will be highlighted and a comparison between the Milstein and the Huang pincer systems will be discussed to provide theoretical and conceptual insights.
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ISSN:1359-7345
1364-548X
1364-548X
DOI:10.1039/D1CC00528F