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Ruthenium(II) complexes with ferrocene-modified arene ligands: synthesis and electrochemistry
Auteur(s)
Vieille-Petit, Ludovic
Jeanneret-Gris, Julie
Štěpnička, Petr
Date de parution
2004
In
Journal of Organometallic Chemistry, Elsevier, 2004/689/15/2456-2463
Résumé
A series of arene–ruthenium complexes of the general formula [RuCl<sub>2</sub>{η<sup>6</sup>-C<sub>6</sub>H<sub>5</sub> (CH<sub>2</sub>)<sub>2</sub>R}L] with R=OH, CH<sub>2</sub>OH, OC(O)Fc, CH<sub>2</sub>OC(O)Fc (Fc=ferrocenyl) and L=PPh<sub>3</sub>, (diphenylphosphino)ferrocene, or bridging 1,1′-bis(diphenylphosphino)ferrocene, have been synthesized. Two synthetic pathways have been used for these ferrocene-modified arene–ruthenium complexes: (a) esterification of ferrocene carboxylic acid with 2-(cyclohexa-1,4-dienyl)ethanol, followed by condensation with RuCl<sub>3</sub> • <i>n</i>H<sub>2</sub>O to afford [RuCl<sub>2</sub>{η<sup>6</sup>-C<sub>6</sub>H<sub>5</sub> (CH<sub>2</sub>)<sub>2</sub>OC(O)Fc}]<sub>2</sub>, and (b) esterification between ferrocene carboxylic acid and [RuCl<sub>2</sub>{η<sup>6</sup>-C<sub>6</sub>H<sub>5</sub> (CH<sub>2</sub>)<sub>3</sub>OH}L] to give [RuCl<sub>2</sub>{η<sup>6</sup>-C<sub>6</sub>H<sub>5</sub> (CH<sub>2</sub>)<sub>3</sub>OC(O)Fc}L]. All new compounds have been characterized by NMR and IR spectroscopy as well as by mass spectrometry. The single-crystal X-ray structure analysis of [RuCl<sub>2</sub>{η<sup>6</sup>-C<sub>6</sub>H<sub>5</sub> (CH<sub>2</sub>)<sub>3</sub>OH}(PPh<sub>3</sub>)] shows that the presence of a CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>OH side-arm allows [RuCl<sub>2</sub>{η<sup>6</sup>-C<sub>6</sub>H<sub>5</sub> (CH<sub>2</sub>)<sub>3</sub>OH}(PPh<sub>3</sub>)] to form an intramolecular hydrogen bond with a chlorine atom. The electrochemical behavior of selected representative compounds has been studied. Complexes with ferrocenylated side arms display the expected cyclic voltammograms, two <i>independent</i> reversible one-electron waves of the Ru(II)/Ru(III) and Fe(II)/Fe(III) redox couples. Introduction of a ferrocenylphosphine onto the ruthenium is reflected by an additonal reversible, one-electron wave due to ferrocene/ferrocenium system which is, however, coupled with the Ru(II)/Ru(III) redox system.
Identifiants
Type de publication
journal article
