Preparation and Reactivity of Mixed-Ligands Hydride Complexes [RuHCl(CO)(PPh3)2{P(OR)3}]

Mixed-ligands hydride complexes [RuHCl(CO)(PPh3)(2){P(OR)(3)}] (2) (R = Me, Et) were prepared by allowing [RuHCl(CO)(PPh3)(3)] (1) to react with an excess of phosphites P(OR)(3) in refluxing benzene. Treatment of hydrides 2 first with triflic acid and next with an excess of hydrazine afforded hydrazine complexes [RuCl(CO)(kappa (1)-NH(2)NHR1)(PPh3)(2){P(OR)(3)}]BPh4 (3, 4) (R1 = H, CH3). Diethylcyanamide derivatives [RuCl(CO)(N equivalent to CNEt2)(PPh3)(2){P(OR)(3)}]BPh4 (5) were also prepared by reacting 2 first with HOTf and then with N equivalent to CNEt2. The complexes were characterized spectroscopically and by X-ray crystal structure determination of [RuHCl(CO)(PPh3)(2){P(OEt)(3)}] (2b).