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Aromatic Hydrocarbon Cations: Structural Overview01:18

Aromatic Hydrocarbon Cations: Structural Overview

Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
Removing one hydrogen from the intervening CH2 group with both...
Radicals: Electronic Structure and Geometry01:07

Radicals: Electronic Structure and Geometry

This lesson delves into the geometry of a radical, which is influenced by the electronic structure of the molecule. The principle is similar to that of a lone pair, where the unpaired electron influences the geometry at the radical center.
Accordingly, the structure of a trivalent radical lies between the geometries of carbocations and carbanions. An sp2-hybridized carbocation is trigonal planar, while an sp3-hybridized carbanion is trigonal pyramidal. Here, the difference in geometry is...
Radical Reactivity: Steric Effects01:10

Radical Reactivity: Steric Effects

The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the generated carbocation,...
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Carbocations

Carbocations are one of the reaction intermediates formed during several nucleophilic substitutions or elimination reactions. A carbocation is an electron-deficient species with the central carbon atom having six electrons and three bonded atoms. The central carbon in a carbocation is sp2 hybridized with trigonal planar geometry. It has an empty p orbital perpendicular to the plane of the structure that can accept electrons. Thus, carbocations act as strong electrophiles and may react with any...
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Radical Reactivity: Overview

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 molecule. These three...

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Updated: May 12, 2026

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of Phosphorus(I)
08:46

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of Phosphorus(I)

Published on: November 22, 2016

Stable tetraaryldiphosphine radical cation and dication.

Xiaobo Pan1, Yuanting Su, Xiaoyu Chen

  • 1State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.

Journal of the American Chemical Society
|April 5, 2013
PubMed
Summary

Researchers characterized tetraaryldiphosphine radical cation and dication. Oxidation alters geometry from pyramidal to planar, driven by bonding changes and confirmed by EPR and theoretical studies.

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Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
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Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of Phosphorus(I)
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Area of Science:

  • Inorganic Chemistry
  • Organophosphorus Chemistry
  • Physical Chemistry

Background:

  • Tetraaryldiphosphines are versatile phosphorus compounds.
  • Understanding their electronic structure and geometry upon oxidation is crucial for reactivity studies.

Purpose of the Study:

  • To isolate and structurally characterize tetraaryldiphosphine radical cation (1•+) and dication (12+).
  • To investigate the geometric and electronic changes upon oxidation.
  • To rationalize the observed structural alterations based on bonding principles.

Main Methods:

  • Isolation and structural characterization of radical cation and dication salts.
  • Electron Paramagnetic Resonance (EPR) spectroscopy.
  • Theoretical calculations (e.g., DFT).

Main Results:

  • Tetraaryldiphosphine radical cation (1•+) exhibits a relaxed pyramidal geometry.
  • Tetraaryldiphosphine dication (12+) adopts a planar, olefin-like geometry with a P-P π bond.
  • EPR spectroscopy indicates spin density localization on phosphorus atoms in the radical cation.
  • Theoretical calculations support the spin density distribution and geometric preferences.

Conclusions:

  • Oxidation significantly alters the geometry of tetraaryldiphosphines.
  • The observed geometric changes are driven by changes in electronic structure and bonding.
  • The radical cation and dication species display distinct structural and electronic properties.