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Bulky 1,1'-bisphosphanoferrocenes and their coordination behaviour towards Cu(i).

Subhayan DeyDániel BuzsákiClemens BruhnZsolt KelemenRudolf Pietschnig
Published in: Dalton transactions (Cambridge, England : 2003) (2020)
Two bulky mesityl substituted dppf-analogues Fe(C5H4PMes2)2 (Mes = 2,4,6-Me3C6H2, 1) and Fe(C5H4PMes2)(C5H4PPh2) (Mes = 2,4,6-Me3C6H2, Ph = C6H5, 3) have been prepared and their properties as donor ligands have been explored using heteronuclear NMR spectroscopy and in particular via1JP-Se coupling, cyclic voltammetry and DFT calculations. Based on the results obtained, a series of mono- and dinuclear Cu(i) complexes have been prepared with these new diphosphane ligands using Br-, I-, and BF4- as counter anions. For the very bulky ligand 1 rare and unprecedented double bridging complexation modes have been observed containing two non-planar Cu2Br2 units, while for the other dinuclear complexes planar Cu2Br2 units have been found. The Cu(i) complexes of 1 and 3 were then used as catalysts for CO2-fixation reaction with terminal alkynes, and complexes with ligand 3 were found to be more efficient than those with 1. DFT calculations performed on compounds 1, 3 and their Cu(i) complexes were able to verify the trend of these catalytic reactions.
Keyphrases
  • metal organic framework
  • aqueous solution
  • density functional theory
  • molecular docking
  • molecular dynamics
  • molecular dynamics simulations
  • ionic liquid
  • highly efficient
  • room temperature