RESUMO
The mononuclear blue complex [Ru(III)L] (1) where L represents the trianion of 1,4,7-tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane has been synthesized by the reaction of H(3)L.3HPF(6) with [Ru(II)Cl(2)(dmso)(4)] in refluxing CH(3)OH in the presence of air. Chemical or electrochemical oxidation of 1 generates [Ru(II)(2)(L-L)](PF(6))(4) (2), a dinuclear species containing two Ru(II) ions and a neutral tris(disulfide) ligand L-L. The reaction of 1 with 1 equiv of [Ru(II)Cl(2)(dmso)(4)] produces the trinuclear species [LRuRuRuL](PF(6))(2) (3) in low yield. Complexes 2 and 3 have been structurally characterized by X-ray crystallography: [Ru(II)(2)(L-L)](BPh(4))(4).10CH(3)CN, C(194)H(218)B(4)N(16)Ru(2)S(6), crystallizes in the monoclinic space group C2/c with a = 28.734(5) Å, b = 16.347(3) Å, c = 37.986(7) Å, beta = 102.35(2) degrees, and Z = 4 whereas [LRuRuRuL](PF(6))(2).H(2)O, C(78)H(110)F(12)N(6)OP(2)Ru(3)S(6), crystallizes in the monoclinic space group P2(1)/n with a = 18.755(4) Å, b = 22.278(4) Å, c = 21.920(4) Å, beta = 91.69(3) Å, and Z = 4. The electro- and spectroelectrochemistry of 1-3 have been studied in detail as have their electronic structures by (1)H NMR, EPR, UV-vis, IR, and Raman spectroscopy.
