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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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Equilibrium calculations for systems involving multiple equilibria are often complex. For example, to calculate the solubility of a sparingly soluble salt in an aqueous solution in the presence of a common ion, one must consider all the equilibria in this solution. Calculations for these systems can be complicated and tedious, so a systematic approach with a series of steps is often helpful. The process is detailed below.
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Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.
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Stable Mg2+ Dication Weakly Stabilized/Coordinated in Solution: Synthesis, Structure, Reactivity, and Use in

Xuejuan Xu1, Alain Chaumont2, Christophe Gourlaouen2

  • 1Institute of Chemistry, Université de Strasbourg, CNRS, Strasbourg, 67000, France.

Angewandte Chemie (International Ed. in English)
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PubMed
Summary

This study introduces a novel soluble magnesium dication stabilized by carborane anions, enabling new catalytic reactions. This magnesium complex effectively catalyzes alkene/alkyne hydrosilylation and CO2 hydrogenation.

Keywords:
Electrophilic speciesHydrogenationHydrosilylationLewis acidsMagnesium

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Area of Science:

  • Organometallic Chemistry
  • Catalysis
  • Supramolecular Chemistry

Background:

  • Development of stable, soluble magnesium complexes is crucial for advancing homogeneous catalysis.
  • Weakly coordinating anions are key to stabilizing reactive metal centers.
  • Understanding cation-anion interactions is vital for predicting reactivity.

Purpose of the Study:

  • To synthesize and characterize the first soluble and stable Mg(II) dication stabilized by carborane anions.
  • To investigate the catalytic activity of this novel magnesium complex in various organic transformations.
  • To elucidate the structure-activity relationship by comparing with a related ammoniododecaborate salt.

Main Methods:

  • Synthesis of Mg[HexCB11Cl11]2 via reaction of Mg(nBu)2 with [Ph3C][HexCB11Cl11].
  • Solid-state structural analysis and solution-state experimental studies.
  • Classical molecular dynamics simulations (cMD) to probe cation-anion interactions.
  • Catalytic testing for polymerization, hydrosilylation, hydrogenation, and CO2 reduction.

Main Results:

  • Successfully synthesized and characterized the stable Mg(II) dication complex, Mg[HexCB11Cl11]2 (1).
  • Experimental and computational data confirmed retained cation-anion association in solution due to Mg's high electrophilicity.
  • Complex 1 demonstrated catalytic activity in 1-hexene polymerization, alkyne coordination, alkene/alkyne hydrosilylation, CO2 hydrosilylation to methane, transfer hydrogenation, and imine hydrogenation.
  • A comparative study showed Mg[(nBu)3NB12H4Cl7]2 (2), with a more basic anion, exhibited lower Lewis acidity and reduced reactivity.

Conclusions:

  • The novel Mg(II) dication stabilized by [HexCB11Cl11]- anions represents a significant advancement in magnesium chemistry.
  • The complex exhibits versatile catalytic properties, driven by the balance of Mg electrophilicity and weak anion interactions.
  • This work opens new avenues for utilizing magnesium complexes as efficient and tunable catalysts in organic synthesis.