Hexamethylbenzeneruthenium(II) complexes containing bis(diphenylphosphine)amine and their sulphur or selenium derivatives as ligands.

Reaction of dinuclear complex [{(eta(6)-C6Me6) Ru(mu-Cl)Cl}(2)] with the li gand NH(PPh2)(2) in 1:2 molar ratio affords the mononuclear complex [(h(6)- C6Me6)RuCl2{h1-(PPh2)(2)NH}](1) which in turn reacts with AgPF6 to yield th e cationic compound [(h(6)-C6Me6) RuCl{h(2)-(PPh2)(2)NH}]PF6(2). Complex 3 reacts with KOBut to give the neutral complex [(h(6)-C6Me6) RuCl{h(2)-(PPh2 )(2)N}] (3). The anionic ligand of complex 3 reacts easily with HBF4 regene rating the starting complex and with Mel by N-methylation of the chelate li gand. The non coordinating P atom of complex 1 reacts with sulfur or seleni um to form the P-coordinate monosulphide or selenide ligands, [{(h(6)-C6Me6 )RuCl2{h(1)PPh(2)NHP(E)Ph-2}] (5,6). The treatment of complexes 5 and 6 wit h AgPFG 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 Mel.