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Related Concept Videos

Nucleophilic Aromatic Substitution: Elimination–Addition01:11

Nucleophilic Aromatic Substitution: Elimination–Addition

Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is confirmed through isotopic...
Elimination Reactions02:25

Elimination Reactions

A nucleophile can react with an alkyl halide to give the substitution product by displacing the halogen. Or it can function as a base to give the elimination product by deprotonation of the neighboring carbon to form an alkene. In an elimination reaction, the substrate loses two groups from adjacent carbons forming at least one π bond. The carbon attached to the halogen is called the α carbon, while the adjacent carbon is called the β carbon; hence, these reactions are called β elimination or...
E2 Reaction: Stereochemistry and Regiochemistry02:43

E2 Reaction: Stereochemistry and Regiochemistry

Elimination reactions of alkyl halides can yield one or more alkenes depending on the specific regiochemical and stereochemical considerations. While the regiochemistry of the reaction governs the location of the double bond in the product, the stereochemical requirements often influence the geometry.
When a substrate with two different β hydrogens undergoes an E2 elimination, the presence of a strong base can yield two regioisomeric alkenes. The more-substituted alkene is the major product and...
E1 Reaction: Kinetics and Mechanism02:46

E1 Reaction: Kinetics and Mechanism

Here, in contrast to the E2 reaction mechanism, we delve into the aspects of the E1 reaction mechanism, which has two steps: rate-limiting loss of the leaving group and abstraction of the beta hydrogen by a weak base. Typically, the experimental proof for the E1 mechanism is via kinetic studies or isotope studies. While the former demonstrates the first-order kinetics—the dependence of the reaction solely on substrate concentration—the latter proves the abstraction of hydrogen only in the...
Nucleophilic Aromatic Substitution: Addition–Elimination (SNAr)01:30

Nucleophilic Aromatic Substitution: Addition–Elimination (SNAr)

Nucleophilic substitution in aromatic compounds is feasible in substrates bearing strong electron-withdrawing substituents positioned ortho or para to the leaving group. The reaction proceeds via two steps: the addition of the nucleophile and the elimination of the leaving group.
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between the...
Radical Formation: Elimination00:51

Radical Formation: Elimination

Another method of radical formation is the elimination process. It is the opposite of the addition route and is driven by the instability of the radical. For example, as depicted in Figure 1, dibenzoyl peroxide yields a pair of unstable radicals upon homolysis. Given its instability, this radical spontaneously undergoes elimination via a C–C bond cleavage to form a relatively more stable phenyl radical. The mechanism involves cleavage of the bond between the α and β positions with respect to...

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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
10:51

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

Published on: April 10, 2015

Theoretical studies on beta-aryl elimination from Rh(I) complexes.

Liqin Xue1, Ka Chun Ng, Zhenyang Lin

  • 1Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong.

Dalton Transactions (Cambridge, England : 2003)
|July 23, 2009
PubMed
Summary

Density functional theory calculations reveal beta-aryl elimination barriers in rhodium complexes are 20-25 kcal mol(-1). Beta-allyl elimination is more favorable, while beta-vinyl elimination is only slightly more favorable than beta-aryl elimination.

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Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
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Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex

Published on: July 27, 2022

Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction
10:39

Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction

Published on: August 23, 2018

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Last Updated: Jun 21, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
10:51

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

Published on: April 10, 2015

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
10:52

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex

Published on: July 27, 2022

Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction
10:39

Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction

Published on: August 23, 2018

Area of Science:

  • Organometallic Chemistry
  • Computational Chemistry
  • Reaction Mechanisms

Background:

  • Beta-elimination reactions are crucial in organometallic chemistry.
  • Understanding the factors governing these reactions is key to catalyst design.
  • Rhodium complexes are widely used in catalysis, making their reaction mechanisms important.

Purpose of the Study:

  • To investigate the energetics and mechanisms of beta-aryl, beta-allyl, and beta-vinyl eliminations in rhodium complexes.
  • To compare the relative stabilities and reaction barriers of these different beta-elimination pathways.
  • To explore the factors influencing the thermodynamic preference between beta-aryl elimination and its reversible insertion reaction.

Main Methods:

  • Density Functional Theory (DFT) calculations using the Becke3LYP functional.
  • Computational modeling of rhodium alkoxide, alkyl, and amido complexes.
  • Thermodynamic analysis of reaction pathways.

Main Results:

  • Typical barriers for beta-aryl eliminations were calculated to be in the range of 20-25 kcal mol(-1).
  • Beta-allyl elimination was found to be significantly more favorable than beta-aryl elimination.
  • Beta-vinyl elimination was only slightly more favorable than beta-aryl elimination.
  • The reversible beta-aryl elimination corresponds to insertion into a metal-aryl bond.

Conclusions:

  • The relative favorability of beta-elimination pathways depends on the nature of the beta-substituent (aryl, allyl, vinyl).
  • The thermodynamic preference between beta-aryl elimination and metal-aryl bond insertion can be tuned by altering substrates and ligands.
  • DFT calculations provide valuable insights into the intricate reaction mechanisms of organometallic complexes.