Redox chemistry of (1,4,7-tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyelononane)ruthenium(III), [(RuL)-L-III]: Synthesis and characterization of [Ru-2(II)(L-L)](BPh4)(4)center dot 10CH(3)CN and [LRuRuRuL](PF6)(2)centerdot H2O

The mononuclear blue complex [(RuL)-L-III] (1) where L represents the trian ion of 1,4,7-tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane ha s been synthesized by the reaction of H3L . 3HPF(6) with [(RuCl2)-Cl-II(dms o)(4)] in refluxing CH3OH in the presence of air. Chemical or electrochemic al oxidation of 1 generates [Ru-2(II)(L-L)](PF6)(4) (2), a dinuclear specie s containing two Run ions and a neutral tris(disulfide) ligand L-L. The rea ction of 1 with 1 equiv of [(RuCl2)-Cl-II(dmso)(4)] produces the trinuclear species [LRuRuRuL](PF6)(2) (3) in low yield. Complexes 2 and 3 have been s tructurally characterized by X-ray crystallography: [Ru-2(II)(L-L)](BPh4)(4 ). 10CH(3)CN, C194H218B4N16Ru2S6, crystallizes in the monoclinic space grou p C2/c with a = 28.734(5) Angstrom, b = 16.347(3) Angstrom, c = 37.986(7) A ngstrom, beta = 102.35(2)degrees, and Z = 4 whereas [LRuRuRuL](PF6)(2). H2O , C78H110F12N6OP2Ru3S6, crystallizes in the monoclinic space group P2(1)/n with a = 18.755(4) Angstrom, b = 22.278(4) Angstrom, c = 21.920(4) Angstrom , beta = 91.69(3) Angstrom, and Z = 4. The electro- and spectroelectrochemi stry of 1-3 have been studied in detail as have their electronic structures by H-1 NMR, EPR, UV-vis, IR, and Raman spectroscopy.