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Fully Delocalized (Ethynyl)(vinyl)phenylene-Bridged Diruthenium Radical Complexes

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2010

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Piazza, Emmanuel Di
Norel, Lucie
Rigaut, Stéphane

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Organometallics. 2010, 29(22), pp. 5912-5918. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om1007133

Zusammenfassung

Diruthenium complexes (X)(dppe)2Ru−C≡C−1,4-C6H4−CH═CH−RuCl(CO)(PiPr3)2 (X = Cl, 1a; X = C≡CPh, 1b) containing an unsymmetrical (ethynyl)(vinyl)phenylene bridging ligand are compared to their symmetrical 1,4-bis(ethynyl)phenylene- and 1,4-divinylphenylene-bridged congeners and their mononuclear alkynyl precursors. Electrochemical and UV/vis/NIR, IR, and EPR spectroscopic studies on the neutral complexes and their various oxidized forms indicate bridging ligand-centered oxidation processes and uniform charge and spin delocalization over both dislike organoruthenium moieties despite differences in their intrinsic redox potentials. Comparison between the chloro and the phenylacetylide-terminated derivatives 1a,b suggests further that the conjugated organometallic π-system extends over the entire unsaturated backbone including the terminal ligand at the alkynyl ruthenium site. This paves the way to even more extended π-conjugated organoruthenium arrays for long-range electronic interactions.

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ISO 690PEVNY, Florian, Emmanuel Di PIAZZA, Lucie NOREL, Malte DRESCHER, Rainer F. WINTER, Stéphane RIGAUT, 2010. Fully Delocalized (Ethynyl)(vinyl)phenylene-Bridged Diruthenium Radical Complexes. In: Organometallics. 2010, 29(22), pp. 5912-5918. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om1007133
BibTex
@article{Pevny2010Fully-13614,
  year={2010},
  doi={10.1021/om1007133},
  title={Fully Delocalized (Ethynyl)(vinyl)phenylene-Bridged Diruthenium Radical Complexes},
  number={22},
  volume={29},
  issn={0276-7333},
  journal={Organometallics},
  pages={5912--5918},
  author={Pevny, Florian and Piazza, Emmanuel Di and Norel, Lucie and Drescher, Malte and Winter, Rainer F. and Rigaut, Stéphane}
}
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