Cationic ruthenium(II) complexes containing a chelating η1:η6-phosphinoarene ligand; [RuCl(L)(PPh2(CH2)3-η6-C6H5)][PF6] (L=P(OPh)3, P(OMe)3, PPh3, PMe3, NCMe, NC5H5)

Reactions of the ruthenium(II) complex [RuCl2(PPh2(CH2)3-η6-C6H5)], containing a chelating η1:η6-phosphinoarene ligand, with NH4PF6, in the presence of a variety of neutral two-electron donor ligands, have yielded a series of new cationic complexes of the general formula [RuCl(L)(PPh2(CH2)3-η6-C6H5)][PF6] [L=P(OPh)3 (1), P(OMe)3 (2), PPh3 (3), PMe3 (4), NCMe (5), NC5H5 (6)]. The structures of complexes 3 and 5 have been determined by X-ray crystallography. In all cases 1H- and 13C{1H}-NMR spectra showed characteristic upfield chemical shifts indicative of the presence of a π-bound arene ligand. The η6-C6H5 group displayed five inequivalent resonances in the 1H-NMR spectra, in most cases showing three triplets and two doublets (vicinal coupling, 3JHH=6.4–5.4 Hz) of relative intensities 1:1:1:1:1 and six peaks were observed for the η6-C6H5 ligand in the respective 13C{1H}-NMR spectra, consistent with C1 molecular symmetry at the ruthenium centre in solution. Detailed assignment of the η6-arene resonances has been achieved using a collection of 1H–1H COSY and 1H–13C correlation experiments, combined with a consideration of the relative magnetic anisotropic shielding and the trans influence effects attributed to the ligands L.