Redox chemistry of (1,4,7-tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyelononane)ruthenium(III), [RuIIIL]:: Synthesis and characterization of [RuII2(L-L)](BPh4)4•10CH3CN and [LRuRuRuL](PF6)2•H2O

The mononuclear blue complex [(RuL)-L-III] (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 H3L . 3HPF(6) with [(RuCl2)-Cl-II(dmso)(4)] in refluxing CH3OH in the presence of air. Chemical or electrochemical oxidation of 1 generates [Ru-2(II)(L-L)](PF6)(4) (2), a dinuclear species containing two Run ions and a neutral tris(disulfide) ligand L-L. The reaction 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 structurally characterized by X-ray crystallography: [Ru-2(II)(L-L)](BPh4)(4). 10CH(3)CN, C194H218B4N16Ru2S6, crystallizes in the monoclinic space group C2/c with a = 28.734(5) Angstrom, b = 16.347(3) Angstrom, c = 37.986(7) Angstrom, 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 spectroelectrochemistry of 1-3 have been studied in detail as have their electronic structures by H-1 NMR, EPR, UV-vis, IR, and Raman spectroscopy.