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Pericyclic Reactions: Introduction01:17

Pericyclic Reactions: Introduction

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Pericyclic reactions are organic reactions that occur via a concerted mechanism without generating any intermediates. The reactions proceed through the movement of electrons in a closed loop to form a cyclic transition state, where rearrangement of the σ and π bonds yields specific products.
Pericyclic reactions can be classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions and sigmatropic...
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Thermal and Photochemical Electrocyclic Reactions: Overview01:26

Thermal and Photochemical Electrocyclic Reactions: Overview

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Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
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Thermal Electrocyclic Reactions: Stereochemistry01:17

Thermal Electrocyclic Reactions: Stereochemistry

2.1K
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
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Radical Reactivity: Overview01:11

Radical Reactivity: Overview

2.1K
Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
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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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Olefin Metathesis Polymerization: Overview01:13

Olefin Metathesis Polymerization: Overview

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Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
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Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex.

Journal of visualized experiments : JoVEยท2022
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Related Experiment Video

Updated: Sep 1, 2025

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

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Dynamic Processes of Rhenium Polyhydride Complexes.

Datta V Naik1, Gregory A Moehring1

  • 1Department of Chemistry and Physics, Monmouth University, West Long Branch, NJ 07764, USA.

Molecules (Basel, Switzerland)
|August 12, 2022
PubMed
Summary

High-coordination-number rhenium polyhydride complexes are key to new catalysts for organic molecule transformation. Understanding their dynamic processes is crucial for designing better catalysts with identifiable atomic properties.

Keywords:
dynamic processesline shape fittingpolyhydrideproton exchangepseudorotationrheniumsteric inversionturnstile exchange

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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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Area of Science:

  • Inorganic Chemistry
  • Catalysis
  • Materials Science

Background:

  • High-coordination-number rhenium polyhydride complexes serve as precursors for catalysts.
  • These catalysts are effective in transforming various organic molecules.
  • Limited understanding exists regarding the reaction mechanisms of these transformations.

Purpose of the Study:

  • To review the dynamic processes in high-coordination-number rhenium polyhydride complexes.
  • To explore how understanding these dynamics can aid in designing new catalytic precursors.
  • To enable better identification of individual atom chemical properties in solution.

Main Methods:

  • Literature review of studies on rhenium polyhydride complexes.
  • Analysis of dynamic processes within these complexes.
  • Correlation of dynamic processes with catalytic precursor design.

Main Results:

  • Rhenium polyhydride complexes exhibit complex dynamic behaviors in solution.
  • These dynamic processes complicate the characterization of individual atom properties.
  • Knowledge of these dynamics is essential for targeted catalyst precursor development.

Conclusions:

  • Dynamic processes in high-coordination-number rhenium polyhydride complexes are significant.
  • Further research into these dynamics can lead to improved catalyst design.
  • Future catalysts may feature more readily identifiable atomic properties at room temperature.