Abstract
Electron transfer to a ligand field excited state of tris(glycinato)cobalt(III) by hexacyanoruthenium(II) was observed in pH 5 acetate-buffered aqueous solution. A product of the reaction is a species that has an intervalence transfer band at 9.1 x 10/sup 3/ cm/sup -1/ (1094 nm) with a molar absorptivity of about 7 x 10/sup 3/ M/sup -1/ cm/sup -1/. The same spectroscopic band results from chemical oxidation (H/sub 2/O/sub 2/, Ce/sup 4 +/), anodic oxidation (Pt electrode), and excited-state electron transfer to tris(2,2'-bipyridine) ruthenium(II). Steady-state analysis of the kinetics of the reaction leads to an estimation of the lifetime of the excited state of tris(glycinato)cobalt(III) as 23 +/- 4 ns. The most likely species responsible for the infrared band is the cyanide-bridged dimer ((CN)/sub 5/Ru/sup II/-CN-Ru/sup III/(CN)/sub 5/)/sup 6 -/. The kinetics of its formation from hexacyanoruthenium(II) and -(III) are rapid (second-order rate constant approx. 1 x 10/sup 4/ M/sup -1/ s/sup -1/) in contrast to recent observations on nonphotochemical reactions of hexacyanoruthenium(III).
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