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Temperature-dependent electron shuffle in molecular Group 13/15 intermetallic complexes.

Chelladurai Ganesamoorthy1, Dieter Bläser, Christoph Wölper

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Summary

Monovalent aluminum (Al) and gallium (Ga) compounds react with antimony (Sb) and bismuth (Bi) compounds, forming new organometallic complexes. Indium (In) compounds showed selective reactivity with bismuth, highlighting group trends in these reactions.

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Group 13 elementsdonor-acceptor systemsheterometallic complexesmain-group elementsmetal-metal interactions

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Area of Science:

  • Organometallic chemistry
  • Main group element chemistry
  • Low-coordinate main group compounds

Background:

  • Monovalent main group compounds offer unique reactivity due to their electron deficiency.
  • The E-E bond cleavage in heavier pnictogen compounds (E=Sb, Bi) is a key step in forming novel organometallic structures.
  • Understanding the reactivity trends within Group 13 elements (Al, Ga, In) is crucial for designing new synthetic pathways.

Purpose of the Study:

  • To investigate the reactions of monovalent aluminum (Al), gallium (Ga), and indium (In) complexes with dialkylantimony (Sb2Et4) and dialkylbismuth (Bi2Et4) compounds.
  • To explore the insertion of these pnictogen elements into the metal-ligand framework.
  • To determine the influence of the metal (Al, Ga, In) and the pnictogen (Sb, Bi) on the reaction outcome and stability of the products.

Main Methods:

  • Synthesis of monovalent organoaluminum (RAl), organogallium (RGa), and organoindium (RIn) precursors.
  • Reaction of these precursors with E2Et4 (E=Sb, Bi) under inert atmosphere conditions.
  • Characterization of reaction products using spectroscopic techniques (e.g., NMR) and potentially X-ray crystallography.

Main Results:

  • Monovalent RAl reacted with E2Et4 to form RAl(EEt2)2 (E=Sb, Bi).
  • Reactions of RGa with E2Et4 resulted in temperature-dependent equilibria between RGa(EEt2)2 and starting materials.
  • RIn did not react with Sb2Et4 but formed RIn(BiEt2)2 at low temperatures with Bi2Et4.

Conclusions:

  • Monovalent Al and Ga exhibit insertion reactivity into E-E bonds of Sb and Bi compounds, with Ga showing equilibrium behavior.
  • Indium displays selective reactivity, reacting only with Bi2Et4 under specific conditions.
  • These findings illustrate distinct reactivity patterns for Group 13 elements with heavier pnictogens, influenced by metal identity and reaction conditions.