Abstract
The preparation of the mononuclear (Ru(bpy)/sub 2/L)/sup 2 +/ (L = bpy, phenOCH/sub 3/, phenC(==O)NH-n-C/sub 3/H/sub 7/), the binuclear ((bpy)/sub 2/RuLRu(bpy)/sub 2/)/sup 4 +/ (L = phenO(CH/sub 2/CH/sub 2/O)/sub n/phen (n = 2-4), phenC(==O)NHCH/sub 2/CH/sub 2/O)/sub n/(CH/sub 2/CH/sub 2/NH(O==)Cphen (n = 1,2), phenC(==O)NH(CH/sub 2/)/sub n/NH(O==)Cphen (n = 3,6)), and the trinuclear (N(CH/sub 2/CH/sub 2/OphenRu(bpy)/sub 2/)/sub 3/)/sup 6 +/ is described. Both the mononuclear and the binuclear complexes exhibit at a platinum electrode one oxidation wave and three reduction waves at potentials close to those observed for Ru(bpy)/sub 3//sup 2 +/. The oxidation and the reductions of the binuclear complexes are two-electron-transfer reactions. From the reduction of the peak width of the differential pulse polarograms it is concluded that K/sub con/less than or equal to 1 for the conproportionation equilibrium (2,2) + (3,3) in equilibrium 2(2,3). The mixed-valence 5+ ion has an intervalence-transfer band in the solid state (KBr) in the near-infrared spectral region. Given the saturated character of the bridge, this represents a clear example of an intramolecular outer-sphere electron-transfer transition.
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