Bimetallic ruthenium-tin chemistry: Synthesis and molecular structure of arene ruthenium complexes containing trichlorostannyl ligands

A series of neutral, anionic and cationic arene ruthenium complexes contg. the trichlorostannyl ligand were synthesized from SnCl2 and the corresponding arene ruthenium dichloride dimers [(?6-arene)Ru(?2-Cl)Cl]2 (arene = C6H6, PriC6H4Me). While the reaction with triphenylphosphine and stannous chloride only gives the neutral mono(trichlorostannyl) complexes [(?6-C6H6)Ru(PPh3)(SnCl3)Cl] (1) and [(?6-PriC6H4Me)Ru(PPh3)(SnCl3)Cl] (2), the neutral di(trichlorostannyl) complex [(?6-PriC6H4Me)Ru(NCPh)(SnCl3)2] (3) could be obtained for the para-cymene deriv. with benzonitrile as addnl. ligand. By contrast, the analogous reaction with the benzene deriv. leads to a salt composed of the cationic mono(trichlorostannyl) complex [(?6-C6H6)Ru(NCPh)2(SnCl3)]+ (5) and of the anionic tris(trichlorostannyl) complex [(?6-C6H6)Ru(SnCl3)3]- (6). However, [(?6-PriC6H4Me)Ru(?2-Cl)Cl]2 reacts with SnCl2 and hexamethylenetetramine hydrochloride or 18-crown-6 to give the anionic di(trichlorostannyl) complex [(?6-PriC6H4Me)Ru(SnCl3)2Cl]- (4), isolated as the hexamethylenetetrammonium salt or the chloro-tin 18-crown-6 salt. The single-crystal x-ray structure analyses of 1, 2, [(CH2)6N4H][4], [(18-crown-6)SnCl][4] and [5][6] reveal for all complexes a pseudo-tetrahedral piano-stool geometry with ruthenium-tin bonds ranging from 2.56 (anionic complexes) to 2.60 Å (cationic complex). [on SciFinder(R)]