Journal
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
Volume 73, Issue 5, Pages 1205-1212Publisher
CHEMICAL SOC JAPAN
DOI: 10.1246/bcsj.73.1205
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A pyrazine bridged dimer of trinuthenium clusters [{(Ru2RuII)-Ru-III(mu(3)-O)(mu-CH3CO2)(6)(CO)(abco)}(2)(mu-pz)] (abco = 1-azabicyclo[2,2,2]octane, pz = pyrazine) gives an inter-cluster mixed valence state upon one electron reduction. The splitting of the reduction waves in cyclic voltammetry, Delta E, was 470 mV. This corresponds to a comproportionation constant for formation of the mixed valence state of 9.0 x 10(7). The IR spectrum of the mixed valence species in the nu(CO) region, measured by reflectance IR spectroelectrochemistry, showed a completely coalesced nu(CO) band. This represents delocalized redox behavior on the infrared vibrational timescale. The rate constant for intramolecular electron transfer was estimated to be 1 x 10(12) s(-1) at -18 degrees C by simulating the nu(CO) absorption bandshape. The mixed valence complex showed an intervalence charge transfer (ICT) band at 12500 cm(-1). Hush analysis provides a spectroscopic estimate of H-AB to be 2490 cm(-1). Crystal structures of [{(Ru2RuII)-Ru-III(mu(3)-O)(mu-CH3CO2)(6)(CO)(abco)}(2)(mu-pz)]. 2CH(2)Cl(2) and its precursor, [(Ru2RuII)-Ru-III(mu(3)-O)(CH3CO2)(6)(CO)(abco)(2)]. CH2Cl2, were determined by X-ray crystallography. Trends in Ru-O(oxo) and Ru-O(acetate) distances in these compounds show that the divalent site is localized on the Ru center attached to the carbonyl ligand.
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