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Bulky cationic β-diketiminate magnesium complexes.

Alexander Friedrich1, Jürgen Pahl, Holger Elsen

  • 1Inorganic and Organometallic Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 1, 91058 Erlangen, Germany. sjoerd.harder@fau.de.

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Summary
This summary is machine-generated.

Bulky cationic magnesium (Mg) complexes featuring the tBuBDI ligand exhibit enhanced Lewis acidity compared to their MeBDI counterparts. Steric bulk influences arene coordination, promoting ring slippage and activating arenes for nucleophilic attack.

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Area of Science:

  • Organometallic Chemistry
  • Coordination Chemistry
  • Catalysis

Background:

  • Cationic magnesium complexes with β-diketiminate (BDI) ligands are of interest due to their potential catalytic applications.
  • Previous studies reported cationic (MeBDI)Mg+ complexes, providing a basis for comparison.
  • The influence of bulky ligands on the properties of metal complexes is a key area in coordination chemistry.

Purpose of the Study:

  • To synthesize and characterize novel cationic β-diketiminate Mg complexes with the bulky tBuBDI ligand.
  • To compare the structural, electronic, and Lewis acidic properties of (tBuBDI)Mg+ complexes with those of (MeBDI)Mg+.
  • To investigate the coordination behavior of arene ligands with these cationic Mg complexes.

Main Methods:

  • Synthesis of cationic Mg complexes via reaction of (tBuBDI)MgnBu with [Ph3C]+[B(C6F5)4]-.
  • X-ray crystallography to determine the solid-state structures of the synthesized complexes.
  • Gutmann-Beckett titration and Density Functional Theory (DFT) calculations to assess Lewis acidity and electronic properties.

Main Results:

  • Novel cationic (tBuBDI)Mg+ complexes with B(C6F5)4- anion were successfully prepared.
  • Crystal structures revealed unique interactions, including a short Mg-Cl bond in chlorobenzene solvates and η2-arene coordination.
  • The (tBuBDI)Mg+ complex demonstrated significantly higher Lewis acidity (AN = 76.0) compared to (MeBDI)Mg+ (AN = 70.3), attributed to increased Mg2+ positive charge and steric effects.
  • Steric bulk of the tBuBDI ligand induced ring slippage in arene coordination (η1-arene), enhancing arene polarization and susceptibility to nucleophilic attack.

Conclusions:

  • The bulky tBuBDI ligand enhances the Lewis acidity of cationic Mg complexes.
  • Steric hindrance in (tBuBDI)Mg+ complexes dictates arene coordination modes and influences reactivity.
  • These findings highlight the role of ligand design in tuning the properties and reactivity of magnesium complexes for potential catalytic applications.