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Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI
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Sb-to-P Metathesis: A Direct Route to Structurally Constrained, Cationic PIII Compound.

Deependra Bawari1, Irina Malahov1, Roman Dobrovetsky1

  • 1School of Chemistry, Raymond and Beverly Sackler Faculty of Exact Sciences, Tel Aviv University, 69978, Tel Aviv, Israel.

Angewandte Chemie (International Ed. in English)
|November 21, 2024
PubMed
Summary
This summary is machine-generated.

A new cationic phosphorus(III) compound, [LP][SbCl4], was synthesized and found to actively participate in reactions with small molecules. Replacing the antimony counter anion ([SbCl4]-) with [CB11H12]- redirected reactivity, highlighting the anion's crucial role.

Keywords:
AntimonyCarbeneCationsPhosphorusSmall-Molecule Activation

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Area of Science:

  • Organometallic chemistry
  • Main group chemistry
  • Pincer ligand chemistry

Background:

  • Cationic P(III) compounds are valuable synthetic intermediates.
  • The role of counter anions in reactivity is often overlooked.
  • Pincer ligands offer unique structural and electronic properties.

Purpose of the Study:

  • To synthesize and characterize a structurally constrained cationic P(III) compound with an OCO pincer ligand.
  • To investigate the reactivity of this compound with small molecules like alcohols and amines.
  • To elucidate the role of the counter anion in the observed reactions.

Main Methods:

  • Synthesis via Sb-to-P metathesis reaction.
  • Isolation and characterization of the cationic P(III) compound.
  • Reactivity studies with alcohols and amines using varying counter anions.

Main Results:

  • Successful synthesis of [LP][SbCl4] featuring a carbene donor pincer ligand.
  • Demonstrated that the [SbCl4]- anion is an active participant in reactions, not a spectator.
  • Replacement of [SbCl4]- with [CB11H12]- altered reaction pathways, focusing reactivity on the [LP]+ cation.
  • Observed equilibrium between oxidative addition and ligand-assisted bond activation upon reaction with alcohols and amines.
  • Showcased reversible, thermoneutral activation of PhO-H and PhN(H)-H bonds by the [LP]+ cation.

Conclusions:

  • The [SbCl4]- anion plays a significant role in the reactivity of cationic P(III) compounds.
  • The [LP]+ cation can mediate reversible E-H bond activation.
  • This work provides insights into the design of novel organophosphorus reagents with tunable reactivity.