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Dinuclear hexamethylbenzene ruthenium cations containing η<sup>1</sup>:η<sup>2</sup>-2-(ferrocenyl)ethen-1-yl ligands: Synthesis, structure, electrochemistry
Auteur(s)
Tschan, Mathieu J.-L.
Ludvík, Jiří
Štěpnička, Petr
Date de parution
2006
In
Journal of Organometallic Chemistry, Elsevier, 2006/691/20/4304-4311
Résumé
The cationic ferrocenyl-containing complexes [(η<sup>6</sup>-C<sub>6</sub>Me<sub>6</sub>)<sub>2</sub>Ru<sub>2</sub> (μ-η<sup>1</sup>:η<sup>2</sup>-CH–CHFc)<sub>2</sub> (μ-H)]+ (<b>3</b>) and [(η<sup>6</sup>-C<sub>6</sub>Me<sub>6</sub>)<sub>2</sub>Ru<sub>2</sub> (μ-PPh<sub>2</sub>)(μ-η<sup>1</sup>:η<sup>2</sup>-CH–CHFc)(μ-H)]<sup>+</sup> (<b>4</b>) have been synthesised in ethanol from ethynylferrocene and the dinuclear precursors [(η<sup>6</sup>-C<sub>6</sub>Me<sub>6</sub>)<sub>2</sub>Ru<sub>2</sub> (μ-H)<sub>3</sub>]<sup>+ </sup> (<b>1</b>) and [(η<sup>6</sup>-C<sub>6</sub>Me<sub>6</sub>)<sub>2</sub>Ru<sub>2</sub>(μ-PPh<sub>2</sub>)(μ-H)<sub>2</sub>]<sup>+</sup> (<b>2</b>) respectively, and isolated as tetrafluoroborate salts. The spectroscopic data of <b>3</b> and <b>4</b> as well as the single-crystal X-ray diffraction analysis of [<b>4</b>][BF<sub>4</sub>] show that the alkyne function of ethynylferrocene has been converted to a σ/π-ethenyl ligand by transfer of a bridging hydride from the diruthenium backbone onto the α-carbon of the triple bond in ethynylferrocene. The ferrocenyl-containing diruthenium compounds [<b>3</b>][BF4] and [<b>4</b>][BF4] as well as their parent compounds [<b>1</b>][BF<sub>4</sub>] and [<b>2</b>][BF<sub>4</sub>] have been studied by voltammetric techniques: Whereas <b>1</b> shows only an irreversible Ru(II)/Ru(III) oxidation, the phosphido-bridged derivative <b>2</b> displays two well-separated one-electron redox processes. In the case of <b>3</b> and <b>4</b>, the ferrocenyl substituents give rise to additional reversible ferrocene/ferrocenium waves.
Identifiants
Type de publication
journal article
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