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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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The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael...
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The skeletal structure of polymers synthesized via radical polymerization is always branched. For example, the polymerization of ethylene by radical polymerization results in a low-density grade of polyethylene with a heavily branched skeletal structure. Here, the radical site abstracts hydrogen from the growing chain, and the radical site shifts from the end (a primary carbon center) to anywhere within the growing chain (a secondary carbon center). Consequently, the part of the chain from the...
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The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
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Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is...
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Researchers isolated stable metal unsupported {N4}•- units under ambient conditions, a significant advancement for studying reactive nitrogen species. These persistent molecules show potential as storable nitrogen group transfer reagents.

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Area of Science:

  • * Inorganic Chemistry
  • * Materials Science
  • * Astrochemistry

Background:

  • * Long-chain nitrogen ions and radicals (Nn)x±, n>3, exist in planetary ionospheres.
  • * High reactivity due to N2 loss limits study to extreme pressures (10-200 GPa).

Purpose of the Study:

  • * To isolate and characterize stable metal unsupported {N4}•- units under ambient conditions.
  • * To investigate the bonding, stability, and reactivity of these novel nitrogen species.

Main Methods:

  • * Synthesis of five novel molecules containing {N4}•- units.
  • * Spectroscopic, crystallographic, and computational analyses.
  • * Reactivity studies under ambient conditions.

Main Results:

  • * Isolation of five metal unsupported {N4}•- molecules stable at ambient conditions.
  • * One derivative exhibited multi-week persistence in the solid state.
  • * Characterization revealed insights into {N4}•- chain bonding.
  • * Reactivity studies showed cleavage into N1/N3 fragments and nitrene radical anion formation.

Conclusions:

  • * Demonstrated the isolation of highly reactive nitrogen species under ambient conditions.
  • * {N4}•- units can be stabilized in metal complexes.
  • * Potential applications as storable nitrogen group transfer reagents.