Electron transfer on the infrared vibrational time scale in-the mixed valence state of 1,4-pyrazine- and 4,4 '-bipyridine-bridged ruthenium cluster complexes

Intramolecular electron transfers within the mixed valence states of the li gand bridged hexaruthenium clusters Ru-3(mu(3)-O) (mu-CH3CO2)(6)(CO)(L)(mu- L')Ru-3 (mu(3)-O)(mu(3)-CH3CO2)(6)(CO) CL) (L' = 1,4-pyrazine; L = 4-di-met hylaminopyridine (1), pyridine(2), 4-cyanopyridine (3), or L' = 4,4'-bipyri dine; L = 4-dimethylaminopyridine (4), pyridine (5), 4-cyanopyridine (6)) w ere examined. Two discrete and reversible single electron reductions are ev ident by cyclic voltammetry in the redox chemistry of 1-5, and the interclu ster charge-transfer complexes are well-defined. The splitting of the reduc tion waves, Delta E, is related to the electronic coupling H-AB between the triruthenium clusters, and varies from 80 mV for 5 to 440 mV for 1. In the case of 6, the splitting of the reduction waves, Delta E, is <50 mV and th e intercluster charge-transfer complex is not defined. The mixed Valence st ates of 1-3 also exhibit intervalence charge transfer (ICT) bands in the re gion 12 100 (1) to 10 800 cm(-1) (3) which provide spectroscopic estimates of H-AB in the range 2180 (1) to 1310 cm(-1) (3). The magnitude of the elec tronic coupling H-AB is found to strongly influence the IR spectra of the c m singly reduced (-1) mixed valence states of 1-6 in the nu(CO) region. In the case of relatively weak electronic coupling (4-6), two nu(CO) bands are clearly resolved. In the cases of strong electronic coupling (1-3), these bands broaden to a single nu(CO) absorption band. These data allow the rate constants, k(e), for electron transfer : in the mixed valence states of 1, 2,and 3 to be estimated by simulating dynamical effects (Bloch-type equati ons) on nu(CO) absorption band shape at 9 x 10(11), 5 x 10(11), and ca. 1 x 10(11) s(-1), respectively. The less strongly coupled 4,4'-bipyridine-brid ged complexes 4-6 exhibit IR line shapes in the -1 mixed valence states tha t are not as strongly affected by electron-transfer dynamics. The rate cons tant for the -1 mixed valence state of 4 is close to the lower limit that c an be estimated by this approach, between 1 x 10(10) and I x 10(11) s(-1).