New cationic complexes [Ru(η 5 -C 5 H 5 )(EPh 3 )(L)]BF 4 [L=pyridine-2-carbaldehyde azine (paa); E=P, 1; E=As, 2; E=Sb, 3] and κ 1 bonded dppm complexes [Ru(η 5 -C 5 H 5 )(κ 1 -dppm)(L)]BF 4 [L=paa 4; L=p-phenylene-bis(picoline)aldimine (pbp) 5] containing both group V donor and pyridyl–azine ligand are reported. The complexes were fully characterized by analytical and spectral studies. 31 P NMR spectral studies suggested coordination of dppm in the complexes 4 and 5 in κ 1 -manner, which was further, confirmed by structural studies on the representative complex 4. Weak interaction studies revealed that inter- and intramolecular C–H⋯X (X=O, F, Cl, π) and π–π interactions in the complexes 1 and 4 lead to helical structures.