Cationic complexes of ruthenium-(II) and -(III) with uni- and poly-dentate ligands

Abstract

The reaction of ruthenium(III) perchlorate with some polytertiary phosphines or arsines has been investigated. With bidentate ligands in ethanol cationic complexes of the type [Ru(L–L)₃(ClO₄)]ClO₄(L–L = Ph₂PCH₂PPh₂, Ph₂PCH₂CH₂PPh₂, Ph₂AsCH₂CH₂AsPh₂, or Ph₂AsCH₂CH₂PPh₂) are obtained. With terdentate ligands the complexes obtained are of the type [RuL₂(ClO₄)][ClO₄]₂[L = NH(CH₂CH₂PPh₂)₂ or NH(CH₂CH₂AsPh₂)₂]. The reaction of the complex [RuCl₃(AsPh₃)₂(MeOH)] with AsPh₃ and PPh₃ in the presence of an excess of NaClO₄ in methanol gave [Ru(AsPh₃)₄(ClO₄)₂]ClO₄ and [Ru(AsPh₃)(PPh₃)₃(ClO₄)₂]ClO₄ respectively. With terdentate ligands [RuCl₃(AsPh₃)₂(MeOH)] afforded mixed-ligand cationic complexes of the type [Ru(AsPh₃)₂L(ClO₄)][ClO₄]₂[L = NH(CH₂CH₂PPh₂)₂ or NH(CH₂C₂AsPh₂)₂]. Perchlorate co-ordination is discussed in terms of the i.r. spectra of complexes, and structures are proposed based on the ¹H, ³¹P, and ¹⁴N n.m.r. spectra.