Simultaneous bridge-localized and mixed-valence character in diruthenium radical cations featuring diethynylaromatic bridging ligands. - Université de Rennes Accéder directement au contenu
Article Dans Une Revue Journal of the American Chemical Society Année : 2011

Simultaneous bridge-localized and mixed-valence character in diruthenium radical cations featuring diethynylaromatic bridging ligands.

Mark A. Fox
  • Fonction : Auteur
Rachel L. Roberts
  • Fonction : Auteur
Daniel A. Brue
  • Fonction : Auteur
Dmitry S. Yufit
  • Fonction : Auteur
Judith A. K. Howard
  • Fonction : Auteur
Paul J. Low
  • Fonction : Auteur correspondant
  • PersonId : 945284

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Résumé

A series of bimetallic ruthenium complexes [{Ru(dppe)Cp*}(2)(μ-C≡CArC≡C)] featuring diethynylaromatic bridging ligands (Ar = 1,4-phenylene, 1,4-naphthylene, 9,10-anthrylene) have been prepared and some representative molecular structures determined. A combination of UV-vis-NIR and IR spectroelectrochemical methods and density functional theory (DFT) have been used to demonstrate that one-electron oxidation of compounds [{Ru(dppe)Cp*}(2)(μ-C≡CArC≡C)](HC≡CArC≡CH = 1,4-diethynylbenzene; 1,4-diethynyl-2,5-dimethoxybenzene; 1,4-diethynylnaphthalene; 9,10-diethynylanthracene) yields solutions containing radical cations that exhibit characteristics of both oxidation of the diethynylaromatic portion of the bridge, and a mixed-valence state. The simultaneous population of bridge-oxidized and mixed-valence states is likely related to a number of factors, including orientation of the plane of the aromatic portion of the bridging ligand with respect to the metal d-orbitals of appropriate π-symmetry.
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Dates et versions

hal-00859838 , version 1 (09-09-2013)

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Mark A. Fox, Boris Le Guennic, Rachel L. Roberts, Daniel A. Brue, Dmitry S. Yufit, et al.. Simultaneous bridge-localized and mixed-valence character in diruthenium radical cations featuring diethynylaromatic bridging ligands.. Journal of the American Chemical Society, 2011, 133 (45), pp.18433-46. ⟨10.1021/ja207827m⟩. ⟨hal-00859838⟩
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