Options
A Surprising Reaction of Trimethylphosphane with the Unsaturated Diruthenium Complex [(η<sup>6</sup>-C<sub>6</sub>Me<sub>6</sub>)<sub>2</sub>Ru<sub>2</sub> (μ<sub>2</sub>-H)<sub>3</sub>]<sup>+</sup>: Synthesis and Molecular Structure of the Cations [(η<sup>6</sup>-C<sub>6</sub>Me<sub>6</sub>)Ru<sub>2</sub> (PMe<sub>3</sub>)<sub>3</sub> (μ<sub>2</sub>-H)<sub>3</sub>]<sup>+</sup> and [(η<sup>6</sup>-C<sub>6</sub>Me<sub>6</sub>)2Ru<sub>2</sub> (PMe<sub>3</sub>)<sub>2</sub>(μ<sub>2</sub>-H)(H)<sub>2</sub>]<sup>+</sup>
Auteur(s)
Tschan, Mathieu J.-L.
Chérioux, Frédéric
Date de parution
2007
In
European Journal of Inorganic Chemistry, Wiley, 2007/4//509-513
Résumé
Whereas aromatic or aliphatic phosphanes undergo cleavage of the P-C bond in the reaction with [(η<sup>6</sup>-C<sub>6</sub>Me<sub>6</sub>)<sub>2</sub>Ru<sub>2</sub> (μ<sub>2</sub>-H)<sub>3</sub>]<sup>+</sup> to give phosphido-bridged diruthenium cations of the type [(η<sup>6</sup>- C<sub>6</sub>Me<sub>6</sub>)<sub>2</sub>Ru<sub>2</sub>(<sub>2</sub>-PR<sub>2</sub>)(μ<sub>2</sub>-H)<sub>2</sub>]<sup>+</sup>, trimethylphosphane surprisingly yields the substitution product [(η<sup>6</sup>-C<sub>6</sub>Me<sub>6</sub>)Ru<sub>2</sub> (PMe<sub>3</sub>)<sub>3</sub> (μ<sub>2</sub>-H)<sub>3</sub>]<sup>+</sup> (<b>1</b>), as well as the racemic intermediate [(η<sup>6</sup>-C<sub>6</sub>Me<sub>6</sub>)<sub>2</sub>Ru<sub>2</sub>(PMe<sub>3</sub>)<sub>2</sub>(μ<sub>2</sub>-H)(H)<sub>2</sub>]<sup>+</sup> (<b>2</b>), in the form of the tetrafluoroborate salts. In complex <b>2</b>, the hydrido ligands are fluxional in solution, as shown by variable-temperature <sup>1</sup>H NMR spectroscopy. Cation <b>1</b> reacts with <i>p</i>-bromothiophenol to give the complex [(η<sup>6</sup>-C<sub>6</sub>Me<sub>6</sub>)<sub>2</sub>Ru<sub>2</sub> (PMe<sub>3</sub>)<sub>3</sub>{μ<sub>2</sub>-(<i>p</i>-Br-C<sub>6</sub>H<sub>4</sub>)-S}(μ<sub>2</sub>-H)<sub>2</sub>]<sup>+</sup> (<b>3</b>), isolated as the tetrafluoroborate salt.
Identifiants
Type de publication
journal article
