Ruthenium(II) complexes with ferrocene-modified arene ligands: synthesis and electrochemistry

A series of arene–ruthenium complexes of the general formula [RuCl2{g-C6H5(CH2)2R}L] with R1⁄4OH, CH2OH, OC(O)Fc, CH2OC(O)Fc (Fc1⁄4 ferrocenyl) and L1⁄4PPh3, (diphenylphosphino)ferrocene, or bridging 1,10-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 RuCl3 nH2O to afford [RuCl2{g-C6H5(CH2)2OC(O)Fc}]2, and (b) esterification between ferrocene carboxylic acid and [RuCl2{g-C6H5(CH2)3OH}L] to give [RuCl2{g-C6H5(CH2)3OC(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 [RuCl2{g-C6H5(CH2)3OH}(PPh3)] shows that the presence of a CH2CH2CH2OH side-arm allows [RuCl2{g-C6H5(CH2)3OH}(PPh3)] 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 independent 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.