α- and β-Eliminations in Transition Metal Complexes : Strategies to Cleave Unstrained C−C and C−F Bonds
(2021) In Helvetica Chimica Acta 104(11).- Abstract
Oxidative addition is the standard process for single-bond activation in transition metal catalysis and it is known to operate for many types of bonds, but challenging σ-bonds e. g. C(sp3)−F and C(sp3)−C(sp3) bonds are the exceptions in this respect. This short review aims at demonstrating how both α- and β-eliminations may be better options for activation of unstrained C−F and C−C single bonds. Selected examples of such eliminations are presented with a mechanistic focus indicating how unstrained and unactivated C−C and C−F bonds can be broken by employing α- and β-eliminations in transition metal hydrocarbyl ligands. Our examples show that the reaction barrier in β-eliminations is controlled by the... (More)
Oxidative addition is the standard process for single-bond activation in transition metal catalysis and it is known to operate for many types of bonds, but challenging σ-bonds e. g. C(sp3)−F and C(sp3)−C(sp3) bonds are the exceptions in this respect. This short review aims at demonstrating how both α- and β-eliminations may be better options for activation of unstrained C−F and C−C single bonds. Selected examples of such eliminations are presented with a mechanistic focus indicating how unstrained and unactivated C−C and C−F bonds can be broken by employing α- and β-eliminations in transition metal hydrocarbyl ligands. Our examples show that the reaction barrier in β-eliminations is controlled by the s-character of the participating bonds where a higher s-character gives a better overlap in the multi-center transition state thereby increasing the reactivity; still β-aryl eliminations can compete with the classical β-hydrogen eliminations in certain cases.
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- author
- Karimzadeh-Younjali, Morteza LU and Wendt, Ola F. LU
- organization
- publishing date
- 2021
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- cleavage reactions, elimination, insertion, transition metals, unstrained
- in
- Helvetica Chimica Acta
- volume
- 104
- issue
- 11
- publisher
- John Wiley & Sons Inc.
- external identifiers
-
- scopus:85117224321
- ISSN
- 0018-019X
- DOI
- 10.1002/hlca.202100114
- language
- English
- LU publication?
- yes
- additional info
- Publisher Copyright: © 2021 The Authors. Helvetica Chimica Acta published by Wiley-VHCA AG, Zurich, Switzerland
- id
- 9afe88b6-ac85-4f62-a90a-504a7f06154b
- date added to LUP
- 2021-11-05 15:11:41
- date last changed
- 2022-04-19 17:44:34
@article{9afe88b6-ac85-4f62-a90a-504a7f06154b, abstract = {{<p>Oxidative addition is the standard process for single-bond activation in transition metal catalysis and it is known to operate for many types of bonds, but challenging σ-bonds e. g. C(sp<sup>3</sup>)−F and C(sp<sup>3</sup>)−C(sp<sup>3</sup>) bonds are the exceptions in this respect. This short review aims at demonstrating how both α- and β-eliminations may be better options for activation of unstrained C−F and C−C single bonds. Selected examples of such eliminations are presented with a mechanistic focus indicating how unstrained and unactivated C−C and C−F bonds can be broken by employing α- and β-eliminations in transition metal hydrocarbyl ligands. Our examples show that the reaction barrier in β-eliminations is controlled by the s-character of the participating bonds where a higher s-character gives a better overlap in the multi-center transition state thereby increasing the reactivity; still β-aryl eliminations can compete with the classical β-hydrogen eliminations in certain cases.</p>}}, author = {{Karimzadeh-Younjali, Morteza and Wendt, Ola F.}}, issn = {{0018-019X}}, keywords = {{cleavage reactions; elimination; insertion; transition metals; unstrained}}, language = {{eng}}, number = {{11}}, publisher = {{John Wiley & Sons Inc.}}, series = {{Helvetica Chimica Acta}}, title = {{α- and β-Eliminations in Transition Metal Complexes : Strategies to Cleave Unstrained C−C and C−F Bonds}}, url = {{http://dx.doi.org/10.1002/hlca.202100114}}, doi = {{10.1002/hlca.202100114}}, volume = {{104}}, year = {{2021}}, }