Bis(diphenylphosphino)amine and their dichalcogenide derivatives as ligands in rhodium(III), iridium(III), and ruthenium(II) complexes. Crystal structures of [(eta(5)-C5Me5)MCl{eta(2)-(SePPh2)(2)N}] (M = Rh, Ir)

Reaction of the dimers [{(eta(5)-C5Me5)MCl}(2)(mu-Cl)(2)] (M = Rh, Ir) or [ {(eta(6)-arene)RuCl}(2)(mu-Cl)(2)] (arene = p-(MeC6H4Pr)-Pr-i, C6Me6) with NH(PPh2)(2) in the presence of AgA (A = BF4, PF6) leads to the mononuclear cationic complexes [(eta(5)-C5Me5)MCl{eta(2)- (PPh2)(2)NH}]A (M = Rh (1), I r (2)) or [(eta(6)-arene)RuCl{eta(2)-(PPh2)(2)NH}]A (arene = p-(MeC6H4Pr)-P r-i (3), C6Me6 (4)). Similar reactions using the chalcogenide derivatives N H(EPPh2)(2) (E = S, Se) yield the neutral complexes [(eta(5)-C5Me5)RhCl{eta (2)-(EPPh2)(2)N}] (E = S (5), Se (6)), [(eta(5)-C5Me5)IrCl{eta(2)-(EPPh2)(2 )N}] (E = S (7), Se (8)), [(eta(6)-arene)RuCl{eta(2)-(SPPh2)(2)N}] (arene = C6H6 (9), p-(MeC6H4Pr)-Pr-i (10)) and [(eta(6)-arene)RuCl{eta(2)-(SePPh2)( 2)N)}] (arene = C6Me6 (11), p-(MeC6H4Pr)-Pr-i (12)). Chloride abstraction f rom complexes 5-8 with AgPF6 in the presence of PPh3 gives the cationic com plexes [(eta(5)-C5Me5)Rh{eta(2)-(EPPh2)(2)N}(PPh3)]PF6 (E = S (13), Se (14) ) and [(eta(5)-C5Me5)Ir{eta(2)-(EPPh2)(2)N}(PPh3)]PF6 (E = S (15), Se (16)) . Complexes 13-16 can also be synthesised from the starting dinuclear compl exes, AgPF6, NH(EPPh2)(2) and PPh3. Using this alternative synthetic route the related ruthenium complexes [(eta(6)-C6Me6)Ru{eta(2)-(EPPh2)(2)N}(C5H5N )] BF4 (E = S (17), Se (18)) can be prepared. All described compounds have been characterised by microanalysis and NMR (H-1, P-31) and IR spectroscopy . The crystal structures of the neutral complexes [(eta(5)-C5Me5)MCl{eta(2) -(SePPh2)(2)N}] (M = Rh (6), Ir (8)) have been determined by X-ray diffract ion methods. Both complexes exhibit analogous pseudo-octahedral molecular s tructures with a C5Me5 group occupying three coordination positions and a b identate chelate Se,Se'-bonded ligand and a chloride atom completing the co ordination sphere. (C) 2000 Elsevier Science S.A. All rights reserved.