NEW MU-DISULFIDO AND MU-DISELENIDO COMPLEXES OF RUTHENIUM(III) - CRYSTAL-STRUCTURE OF [(LRUIII(ACAC))2(MU-S2)](PF6)2 (L = 1,4,7-TRIMETHYL-1,4,7-TRIAZACYCLONONANE, ACAC = PENTANE-2,4-DIONATE)

Reaction of the mononuclear species [LRu(acac)(OH)]PF6.H2O in alkaline aqueous solution with Na2S.xH2O and H2Se yields the dinuclear species [{LRu(acac)}2(mu-S2)](PF6)2 (1) and [{LRu(acac)}2(mu-Se2)](PF6)2 (2), respectively, where L represents 1,4,7-trimethyl-1,4,7-triazacyclononane and acac = pentane-2,4-dionate. The crystal structure of 1 has been determined by X-ray crystallography at 295 K: triclinic space group P1BAR, a = 8.157(5) angstrom, b = 11.5 26(6) angstrom, c = 12.184(6) angstrom, alpha = 76.11(4)-degrees, beta = 86.52(4)-degrees, gamma = 77.51(4)-degrees, V = 1085.6(15) angstrom3, Z = 1, R = 0.038, and R(w) = 0.035. The Ru-S and S-S bond distances of 2.202(2) and 1.989(2) angstrom, respectively, the electronic spectrum, the electrochemistry, and the diamagnetism of 1 are indicative of an exchange-coupled dinuclear ruthenium(III) species containing an S-2(2-) bridge. Similar results are reported for the mu-diselenido species 2.