Synthesis, Characterization, and Fluxional Behavior of a 34 Electron Homochiral Dimetallic Complex with an Unsupported Hydride Bridge between Two Ru Atoms - Archive ouverte HAL
Article Dans Une Revue Organometallics Année : 2012

Synthesis, Characterization, and Fluxional Behavior of a 34 Electron Homochiral Dimetallic Complex with an Unsupported Hydride Bridge between Two Ru Atoms

Résumé

The binuclear η6-benzene cycloruthenated complex 2, which bears an unsupported bridging hydride ligand, was synthesized by treating the monomeric cationic cycloruthenated (R)-(+)-1-(1-naphthyl)ethylamine 1 with potassium hydroxide under biphasic conditions and then with an alcoholic solvent. Alternatively, compound 2 was prepared from an equimolar amount of compound 1 and the homologous monomeric hydrido complex 3. The crystal structure of 2 revealed π- stacking interactions between the naphthyl groups of each cyclometalated amine; the hydride ligand is bent, with a Ru−H−Ru angle of 145.3(10)°. Compound 2 is fluxional as shown by variable-temperature NMR analysis. DFT analysis of homochiral 2 and of its hypothetical heterochiral counterpart 2* revealed that dispersion-based π−π interactions between the cyclometalated ring are not the only interactions that must be taken into account to rationalize the conformational preference for 2. Indeed, the overall dispersion-based interactions between all the ligands of the connected metallacycles provide an additional 5 to 6 kcal/mol of stabilization energy for 2 regardless whether the π-stacking interactions between the naphthyl rings exist or not.

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Dates et versions

hal-00698475 , version 1 (16-05-2012)

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Jean-Pierre Djukic, Jean-Baptiste Sortais, Laurent Barloy, Nicolas Pannetier, Claude Sirlin, et al.. Synthesis, Characterization, and Fluxional Behavior of a 34 Electron Homochiral Dimetallic Complex with an Unsupported Hydride Bridge between Two Ru Atoms. Organometallics, 2012, 31 (7), pp.2821-2828. ⟨10.1021/om201093y⟩. ⟨hal-00698475⟩
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