Preparation and reactivity of mixed-ligand ruthenium(II) hydride complexes with phosphites and polypyridyls

Chloro complexes RuCl(N-N)P3]BPh4 (1-3) N-N = 2,2'-bipyridine, bpy; 1,10-phenanthroline, phen; 5,5'-dimethyl-2,2'-bipyridine, 5,5'-Me2bpy; P = P(OEt)3, PPh(OEt)2 and PPh2OEt] were prepared by allowing the RuCl4(N-N)].H2O compounds to react with an excess of phosphite in ethanol. The bis(bipyridine) RuCl(bpy)2P(OEt)3]]BPh4 (7) complex was also prepared by reacting RuCl2(bpy)2.2H2O with phosphite and ethanol. Treatment of the chloro complexes 1-3 and 7 with NaBH4 yielded the hydride RuH(N-N)P3]BPh4 (4-6) and RuH(bpy)2P]BPh4 (8) derivatives, which were characterized spectroscopically and by the X-ray crystal structure determination of RuH(bpy)P(OEt)3]3]BPh4 (4a). Protonation reaction of the new hydrides with Br?nsted acid was studied and led to dicationic Ru(eta2-H2)(N-N)P3]2+ (9, 10) and Ru(eta(2-H2)(bpy)2P]2+ (11) dihydrogen derivatives. The presence of the eta2-H2 ligand was indicated by a short T(1 min) value and by the measurements of the J(HD) in the Ru](eta2-HD) isotopomers. From T(1 min) and J(HD) values the H-H distances of the dihydrogen complexes were also calculated. A series of ruthenium complexes, RuL(N-N)P3](BPh4)2 and RuL(bpy)2P](BPh4)2 (P = P(OEt)3; L = H2O, CO, 4-CH3C6H4NC, CH3CN, 4-CH3C6H4CN, PPh(OEt)2], was prepared by substituting the labile eta2-H2 ligand in the 9, 10, 11 derivatives. The reactions of the new hydrides 4-6 and 8 with both mono- and bis(aryldiazonium) cations were studied and led to aryldiazene Ru(C6H5N=NH)(N-N)P3](BPh4)2 (19, 21), Ru(N-N)P3]2(mu-4,4'-NH=NC6H4-C6H4N=NH)](BPh4)4 (20), and Ru(C6H5N=NH)(bpy)2P](BPh4)2 (22) derivatives. Also the heteroallenes CO2 and CS2 reacted with RuH(bpy)2P]BPh4, yielding the formato Rueta1-OC(H)=O](bpy)2P]BPh4 and dithioformato Rueta1-SC(H)=S](bpy)2P]BPh4 derivatives.