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Related Concept Videos

Thermal Electrocyclic Reactions: Stereochemistry01:17

Thermal Electrocyclic Reactions: Stereochemistry

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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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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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Photochemical Electrocyclic Reactions: Stereochemistry01:26

Photochemical Electrocyclic Reactions: Stereochemistry

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The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
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Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)00:53

Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)

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Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
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Anionic Chain-Growth Polymerization: Overview01:20

Anionic Chain-Growth Polymerization: Overview

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The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
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Thermal Sigmatropic Reactions: Overview01:16

Thermal Sigmatropic Reactions: Overview

1.6K
Sigmatropic rearrangements are a class of pericyclic reactions in which a σ bond migrates from one part of a π system to another. These are intramolecular rearrangements where the total number of σ and π bonds remain unchanged.
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Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers
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Anionic depolymerization transition in IrTe2.

Yoon Seok Oh1, J J Yang2, Y Horibe1

  • 1Rutgers Center for Emergent Materials and Department of Physics and Astronomy, Piscataway, New Jersey 08854, USA.

Physical Review Letters
|August 29, 2014
PubMed
Summary
This summary is machine-generated.

Selenium substitution significantly raises the transition temperature of iridium ditelluride (IrTe2) to a diamagnetic state. This unique depolymerization transition is linked to structural changes and bond destabilization, offering new insights into inorganic solids.

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Raman and IR Spectroelectrochemical Methods as Tools to Analyze Conjugated Organic Compounds
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Chemoselective Preparation of 1-Iodoalkynes, 1,2-Diiodoalkenes, and 1,1,2-Triiodoalkenes Based on the Oxidative Iodination of Terminal Alkynes
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Raman and IR Spectroelectrochemical Methods as Tools to Analyze Conjugated Organic Compounds
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Area of Science:

  • Solid-state chemistry
  • Materials science
  • Crystallography

Background:

  • Iridium ditelluride (IrTe2) exhibits a transition to a diamagnetic superstructure at 278 K.
  • Understanding factors influencing phase transitions in transition metal dichalcogenides is crucial for materials design.

Purpose of the Study:

  • To investigate the effect of selenium substitution on the transition temperature and structural properties of iridium ditelluride.
  • To elucidate the mechanism behind the temperature-induced transition in IrTe2.

Main Methods:

  • Synthesis of selenium-substituted iridium ditelluride.
  • Transmission electron microscopy (TEM) for structural analysis.
  • Temperature-dependent magnetic susceptibility measurements.

Main Results:

  • Selenium substitution increased the transition temperature from 278 K to 560 K.
  • TEM revealed a change in structural modulations from q = 1/5(101) to q = 1/6(101) upon substitution.
  • The transition is associated with the destabilization of polymeric Te-Te bonds.

Conclusions:

  • Selenium substitution effectively enhances the transition temperature in IrTe2.
  • The observed transition is a unique temperature-induced depolymerization phenomenon in crystalline inorganic solids.
  • Chemical and hydrostatic pressure also influence this depolymerization transition.