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Stability of Conjugated Dienes01:28

Stability of Conjugated Dienes

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Introduction
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
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Diels–Alder Reaction: Characteristics of Dienes01:29

Diels–Alder Reaction: Characteristics of Dienes

5.7K
The Diels–Alder reaction brings together a diene and a dienophile to form a six-membered ring. Both components have unique characteristics that influence the rate of the reaction.
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable,...
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Electrophilic 1,2- and 1,4-Addition of X2 to 1,3-Butadiene01:14

Electrophilic 1,2- and 1,4-Addition of X2 to 1,3-Butadiene

4.0K
Electrophilic addition of halogens to alkenes proceeds via a cyclic halonium ion to form a 1,2-dihalide or a vicinal dihalide.
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[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction01:16

[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction

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The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
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Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry01:29

Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry

6.6K
Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
6.6K
Nucleophilic Aromatic Substitution: Elimination–Addition01:11

Nucleophilic Aromatic Substitution: Elimination–Addition

5.6K
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...
5.6K

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Related Experiment Video

Updated: Apr 8, 2026

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
10:44

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals

Published on: April 19, 2019

11.9K

Moving toward Ylide-Stabilized Carbenes.

Bitupon Borthakur1, Ashwini K Phukan2

  • 1Department of Chemical Sciences, Tezpur University, Napam-784 028, Assam (India).

Chemistry (Weinheim an Der Bergstrasse, Germany)
|June 30, 2015
PubMed
Summary

Ylide substitution enhances the σ-donating ability of cyclic carbenes. These ylide-containing carbenes exhibit increased stability and basicity, impacting their reactivity in metal complexes.

Keywords:
boroncarbeneselectron donationrhodiumylides

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Area of Science:

  • Organometallic Chemistry
  • Computational Chemistry
  • Organic Chemistry

Background:

  • Cyclic carbenes are versatile ligands in organometallic chemistry.
  • Understanding their electronic properties is crucial for designing new catalysts.
  • Ylide substituents can significantly alter carbene behavior.

Purpose of the Study:

  • To investigate the impact of ylide substitution on cyclic carbene stability.
  • To evaluate the effect of ylide groups on the σ-donating capacity of carbenes.
  • To correlate theoretical findings with experimental observables.

Main Methods:

  • Theoretical study of cyclic carbenes with ylide substituents.
  • Calculation of singlet-triplet energy gaps and stabilization energies.
  • Analysis of the σ-symmetric lone-pair orbital energy and related properties.

Main Results:

  • All studied carbenes possess a stable singlet ground state.
  • Ylide introduction near the carbene carbon atom increases the lone-pair orbital energy.
  • Enhanced σ-donating ability was observed for ylide-containing carbenes.

Conclusions:

  • Ylide substitution effectively enhances the σ-donating ability and stability of cyclic carbenes.
  • Theoretical predictions correlate well with experimental data like proton affinities and nucleophilicity.
  • This work provides insights into designing more effective carbene ligands.