Abstract The reaction of [(η 5 ‐L 3 )Ru(PPh 3 ) 2 Cl], where; L 3 = C 9 H 7 ( 1 ), C 5 Me 5 (Cp*) ( 2 ) with acetonitrile in the presence of [NH 4 ][PF 6 ] yielded cationic complexes [(η 5 ‐L 3 )Ru(PPh 3 ) 2 (CH 3 CN)][PF 6 ]; L 3 = C 9 H 7 ( [3]PF 6 ) and L 3 = C 5 Me 5 ( [4]PF 6 ), respectively. Complexes [3]PF 6 and [4]PF 6 reacts with some polypyridyl ligands viz , 2,3‐bis (α‐pyridyl) pyrazine (bpp), 2,3‐bis (α‐pyridyl) quinoxaline (bpq) yielding the complexes of the formulation [(η 5 ‐L 3 )Ru(PPh 3 )(L 2 )]PF 6 where; L 3 = C 9 H 7 , L 2 = bpp, ( [5]PF 6 ), L 3 = C 9 H 7 , L 2 = bpq, ( [6]PF 6 ); L 3 = C 5 Me 5 , L 2 = bpp, ( [7]PF 6 ) and bpq, ( [8]PF 6 ), respectively. However reaction of [(η 5 ‐C 9 H 7 )Ru(PPh 3 ) 2 (CH 3 CN)][PF 6 ] ( [3]PF 6 ) with the sterically demanding polypyridyl ligands, viz . 2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine (tptz) or tetra‐2‐pyridyl‐1,4‐pyrazine (tppz) leads to the formation of unexpected complexes [Ru(PPh 3 ) 2 (L 2 )(CH 3 CN)][PF 6 ] 2 ; L 2 = tppz ( [9](PF 6 ) 2 ), tptz ( [11](PF 6 ) 2 ) and [Ru(PPh 3 ) 2 (L 2 )Cl][PF 6 ]; L 2 = tppz ( [10]PF 6 ), tptz ( [12]PF 6 ). The complexes were isolated as their hexafluorophosphate salts. They have been characterized on the basis of micro analytical and spectroscopic data. The crystal structures of the representative complexes were established by X‐ray crystallography.