Reaction of dinuclear complex [{(h6-C6Me6)Ru(µ-Cl)Cl} 2] with the ligand NH(PPh2)2 in 1:2 molar ratio affords the mononuclear complex [(h6-C6Me6)RuCl 2{h1-(PPh2)2NH}](1) which in turn reacts with AgPF6 to yield the cationic compound [(h6-C6Me6)RuCl{h 2-(PPh2)2NH}]PF6 (2). Complex 3 reacts with KOBut to give the neutral complex [(h6-C6Me6)RuCl{h 2-(PPh2)2N}](3). The anionic ligand of complex 3 reacts easily with HBF4 regenerating the starting complex and with MeI by N-methylation of the chelate ligand. The non coordinating P atom of complex 1 reacts with sulfur or selenium to form the P-coordinate monosulphide or selenide ligands, [{(h6-C6Me6)RuCl 2{h1PPh2NHP(E)Ph2 }] (5,6). The treatment of complexes 5 and 6 with AgPF6 affords cationic (7,8) or neutral (9,10) complexes depending of the solvent used. The neutral complex 9 can be N-derivatized by reaction with MeI