Novel cofacial bioctahedral complexes of ruthenium: syntheses and properties of the mixed-valence species [LRu2.5(.mu.-X)3Ru2.5L]2+ (X = Cl, Br, I, OH). Crystal structures of [LRu2.5(.mu.-OH)3Ru2.5L](PF6)2.cntdot.H2O and [LRuIV(.mu.-O)3RuIVL](PF6)2.cntdot.H2O (L = 1,4,7-trimethyl-1,4,7-triazacyclononane)

Reaction of RuCl 2 (dmso) 4 with 1,4,7-trimethyl-1,4,7-triazacyclononane (L; C 9 H 21 N 3 ) in ethanol affords red-brown LRu(dmso) x Cl 2 (x=1-2), which reacted with concentrated HX (X=Cl, Br, I) in the presence of air to yield LRuCl 3 •H 2 O, LRuBr 3 , and LRuI 3 . Treatment of these LRuX 3 species with CF 3 SO 3 H yielded gaseous HX and deep blue solutions from which the mixed-valence complexes [L 2 Ru 2 2.5 (μ-X) 3 ](CF 3 SO 3 ) 2 precipitated upon addition of ether. Blue [L 2 Ru 2 2.5 (μ-X) 3 ](PF 6 ) 2 salts (X=Cl, Br, I) were isolated and characterized