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Related Concept Videos

Common Ion Effect03:24

Common Ion Effect

Compared with pure water, the solubility of an ionic compound is less in aqueous solutions containing a common ion (one also produced by dissolution of the ionic compound). This is an example of a phenomenon known as the common ion effect, which is a consequence of the law of mass action that may be explained using Le Châtelier’s principle. Consider the dissolution of silver iodide:
Metal-Ligand Bonds02:51

Metal-Ligand Bonds

The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
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Indirect-Acting Cholinergic Agonists: Chemistry and Structure-Activity Relationship

Indirect-acting cholinergic agonists are agents that interact with the acetylcholinesterase enzyme in the synaptic cleft, preventing the breakdown of acetylcholine into choline and acetate. Consequently, the concentration of acetylcholine in the synaptic cleft increases. These agonists can be classified into reversible and irreversible inhibitors based on their duration of action.
Reversible inhibitors display short to medium durations of action. Short-acting agents include simple alcohols with...
Complexation Equilibria: The Chelate Effect01:19

Complexation Equilibria: The Chelate Effect

In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
Colloidal precipitates01:09

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The high insolubility of some precipitates can result in an unfavorable relative supersaturation. This can lead to colloidal particles with a large surface-to-mass ratio, where adsorption is promoted. For instance, in the precipitation of silver chloride, silver ions are adsorbed on the surface of the colloidal particles, forming a primary layer. This layer attracts ions of opposite charge (such as nitrate ions), forming a diffuse secondary layer of adsorbed ions. This electric double layer...

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Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides
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Lithium cation as radical-polymerization catalyst.

Timothy Clark1

  • 1Computer-Chemie-Centrum der Friedrich-Alexander-Universität Erlangen-Nürnberg, Erlangen, Germany. clark@chemie.uni-erlangen.de

Journal of the American Chemical Society
|August 24, 2006
PubMed
Summary
This summary is machine-generated.

Naked lithium cations catalyze olefin polymerization by promoting radical addition over hydrogen abstraction. This catalytic effect, driven by metal ion complexation, enables efficient chain growth in nonpolar solvents.

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Area of Science:

  • Physical Chemistry
  • Polymer Science
  • Computational Chemistry

Background:

  • Radical polymerization of olefins is often hindered by competing hydrogen atom abstraction.
  • Metal ions can influence reaction pathways in organic synthesis.
  • Previous experimental work suggested lithium salts could promote alkene polymerization.

Purpose of the Study:

  • To investigate the catalytic role of "naked" lithium cations in olefin radical polymerization.
  • To elucidate the mechanism by which lithium cations influence radical addition versus hydrogen abstraction.
  • To computationally support experimental observations of lithium-promoted alkene polymerization.

Main Methods:

  • Density-functional theory (DFT) calculations.
  • Ab initio quantum chemistry calculations (QCISD and CBS-RAD).
  • Computational modeling of reaction pathways and energy barriers.

Main Results:

  • Lithium cation complexation favors alkyl radical addition to olefins over allylic hydrogen abstraction.
  • The addition of triplet dioxygen to olefins is thermoneutral with a low barrier when complexed to lithium.
  • Hydrogen atom abstraction is also favored by lithium complexation but less so than addition.

Conclusions:

  • "Naked" lithium cations act as catalysts for olefin radical polymerization by selectively promoting chain propagation.
  • Lithium-mediated complexation of oxygen facilitates polymerization initiation.
  • The computational findings align with experimental evidence for lithium-promoted alkene polymerization.