Preparation of stannyl complexes of ruthenium and osmium stabilised by polypyridine and phosphite ligands

Trichlorostannyl complexes [M(SnCl3)(bpy)(2)P]BPh4 [M = Ru, P = P(OEt)(3) 1a, PPh(OEt)(2) 1b; M = Os, P = P(OEt)(3) 2; bpy = 2,2 '-bipyridine] were prepared by allowing chloro complexes [MCl(bpy)(2)P]BPh4 to react with SnCl2 in 1,2-dichloroethane. Bis(trichlorostannyl) compounds Ru(SnCl3)(2)(N-N)P-2 [N-N = bpy, P = P(OEt)(3) 3a, PPh(OEt)(2) 3b; N-N = 1,10-phenanthroline (phen), P = P(OEt)(3) 4] were also prepared by reacting [RuCl(N-N)P-3]BPh4 precursors with SnCl2 center dot 2H(2)O in ethanol. Treatment of both mono-1a, 2 and bis 3a trichlorostannyl complexes with NaBH4 afforded mono- and bis(trihydridestannyl) derivatives [M(SnH3)(bpy)(2)P] BPh4 5, 6 and Ru(SnH3)(2)(bpy)P-2 7 [P = P(OEt)(3)], respectively. Treatment of 1a, 2 with MgBrMe gave the trimethylstannyl complexes [M(SnMe3)(bpy)(2)P] BPh4 8, 9, and treatment of 3a afforded the bis(stannyl) Ru(SnClMe2)(2)(bpy)P-2 10 derivative. Alkynylstannyl complexes [M{Sn(C CR)(3)}(bpy)(2)P]BPh4 11-13 and Ru[Sn(C CR)(3)](2)(N-N)P-2 14 - 17 (R = p-tolyl, Bu-t; N-N= bpy, phen) were also prepared by allowing trichlorostannyl compounds 1-4 to react with Li+[RC C](-) in thf. The complexes were characterised spectroscopically and by the X-ray crystal structure determination of [Ru(SnMe3)(bpy)(2){P(OEt)(3)}] BPh4 8 derivative.