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In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
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Kinetically Stabilized Diarylpnictogenium Ions.

Marvin Janssen1, Stefan Mebs2, Jens Beckmann1

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The study compares new stibenium and bismuthenium ions with related compounds, revealing that aryl substituents significantly alter molecular and electronic structures, including bond lengths and LUMO energies.

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Area of Science:

  • Organometallic Chemistry
  • Main Group Chemistry
  • Supramolecular Chemistry

Background:

  • Pnictogenium ions are versatile compounds with tunable properties.
  • Previous studies have explored phosphenium, arsenium, and bis(m-terphenyl) pnictogenium ions.

Purpose of the Study:

  • To synthesize and characterize novel stibenium and bismuthenium ions.
  • To compare the structural and electronic properties of these new ions with existing pnictogenium ions.
  • To investigate the influence of aryl substituents on the properties of pnictogenium ions.

Main Methods:

  • Synthesis of stibenium and bismuthenium ions with a dispiro[fluorene-9,3'-(1',1',7',7'-tetramethyl-s-hydrindacen-4'-yl)-5',9''-fluorene) ligand.
  • Full characterization of the prepared ions.
  • Comparative analysis of structural and electronic properties with related phosphenium, arsenium, and bis(m-terphenyl) pnictogenium ions.

Main Results:

  • Successful preparation and characterization of [RindMesE]+ (E=Sb, Bi) ions.
  • Demonstrated significant impact of aryl substituents on primary E-C bond lengths.
  • Observed substantial effects of substituents on the electronic structures, specifically the Lowest Unoccupied Molecular Orbital (LUMO) energies.

Conclusions:

  • Aryl substituents play a critical role in dictating the molecular and electronic characteristics of pnictogenium ions.
  • The findings provide insights into the structure-property relationships of heavy pnictogen compounds.
  • This research expands the scope of known pnictogenium ion chemistry and their potential applications.