Perutz, Robin Noel orcid.org/0000-0001-6286-0282, Sabo-Etienne, Sylviane and Weller, Andrew orcid.org/0000-0003-1646-8081 (2022) Metathesis by partner interchange in σ-bond ligands:expanding applications of the σ-CAM mechanism. Angewandte Chemie International Edition. e202111462. ISSN 1433-7851
Abstract
In 2007 two of us defined the σ-Complex Assisted Metathesis mechanism (Perutz and Sabo-Etienne, Angew. Chem. Int. Ed. 2007 , 46 , 2578-2592), i.e. the σ-CAM concept. This new approach to reaction mechanisms brought together metathesis reactions involving the formation of a variety of metal-element bonds through partner-interchange of σ-bond complexes. The key concept that defines a σ-CAM process is a single transition state for metathesis that is connected by two intermediates that are σ-bond complexes while the oxidation state of the metal remains constant in precursor, intermediates and product. This mechanism is appropriate in situations where σ-bond complexes have been isolated or computed as well-defined minima. Unlike several other mechanisms, it does not define the nature of the transition state. In this review, we highlight advances in the characterization and dynamic rearrangements of σ-bond complexes, most notably alkane and zincane complexes, but also different geometries of silane and borane complexes. We set out a selection of catalytic and stoichiometric examples of the σ-CAM mechanism that are supported by strong experimental and/or computational evidence. We then draw on these examples to demonstrate that the scope of the σ-CAM mechanism has expanded to classes of reaction not envisaged in 2007 (additional s-bond ligands, agostic complexes, sp 2 -carbon, surfaces). Finally, we provide a critical comparison to alternative mechanisms for metathesis of metal-element bonds.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2021 The Authors |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Funding Information: | Funder Grant number EPSRC EP/M024210/2 |
Depositing User: | Pure (York) |
Date Deposited: | 19 Oct 2021 10:20 |
Last Modified: | 16 Dec 2024 00:15 |
Published Version: | https://doi.org/10.1002/ange.202111462 |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1002/ange.202111462 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:179402 |
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