Stacked nickelocenes: Synthesis, structural characterization, and magnetic properties

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Erscheinungsjahr:
2010
Medientyp:
Text
Schlagworte:
  • Organometallics
  • Ruthenium
  • Ferrocenyl units
  • Ligands
  • Catalysts
  • Organometallics
  • Ruthenium
  • Ferrocenyl units
  • Ligands
  • Catalysts
Beschreibung:
  • The disubstitution of 1,8-diiodonaphthalene (1) with cyclopentadienyl nucleophiles reveals 1,8-(dicyclopentadienyl)naphthalene, which rapidly undergoes Diels-Alder reaction forming 1,8-(3a',4',7',7a'-tetrahydro-4',7'-methanoindene-7a',8'-diyl)-naphthale ne (2). A subsequent retro-Diels-Alder reaction in the presence of sodium hydride yields the disodium salt of 1,8-(dicyclopentadiendiyl)-naphthalene 3. The disodium salt 3 was the starting material to obtain the paramagnetic bisnickelocene derivative 4, which structure was obtained by X-ray structure analysis, revealing two nickelocenes kept together in a stacked fashion by a 1,8-naphthalene clamp. An electronic interaction between the two nickel atoms is found as a result of cyclic voltammetry, indicating five different oxidation states +4, +3, +2, +1, and 0. The magnetic properties of 4 in solution were studied by variable temperature paramagnetic H-1 NMR spectroscopy and Evans method and revealed Curie behavior between 213 and 293 K. The magnetic susceptibility of a powdered sample of 4 was measured, and an antiferromagnetic interaction with an exchange coupling of J(12) = -31.49 cm(-1) is found. In accord with experimental data, broken symmetry density functional theory (DFT) calculations revealed four antiferromagnetically coupled electrons resulting in an open shell singlet ground state.
Lizenz:
  • info:eu-repo/semantics/restrictedAccess
Quellsystem:
Forschungsinformationssystem der UHH

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