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Lookup NU author(s): Craig Wright, Emeritus Prof Alfred Sykes
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From electrochemical studies, the thermodynamic stability of the mixed valence (one electron reduced) state and the electronic coupling between linked Ru3 units, was studied in the series of the ligand bridged hexaruthernium clusters, [Ru3(μ3-O)(μ-CH3CO2)6(CO)(L)(μ-BL)Ru3(μ3-O)-(μ-CH3CO2)6(CO)(L) ] (BL = pyrazine: L = 4-dimethyl-aminopyridine (dmap) (1a), pyridine (py) (1b), 4-cyanopyridine (cpy) (1c), 1-azabicyclo[2.2.2]octane (1d); BL = 4,4'-bipyridine: L = dmap (2a), py (2b), cpy (2c); BL = 2,7-diazapyrene: L = dmap (3a); BL = 1,4-diazabicyclo-[2.2.2]octane: L = dmap (4a), py (4b), cpy (4c)). The mixed valence states undergoing the most rapid intramolecular electron transfers were observed by reflectance IR spectroelectrochemistry. By simulating dynamical effects on the observed v(CO) absorption bandshapes, the rate constants, k(e), for electron transfer in the mixed valence states of 1a, 1b, 1c and 1d were estimated to be 9 x 1011 s-1 (at room temperature (rt)), 5 x 1011 s-1 (at rt), ca. 1 x 1011 s-1 (at rt), and 1 x 1012 s-1 (at -18 °C), respectively. The rate constant for the -1 mixed valence state of 2a is close to the lower limit that can be estimated by this approach, between 1 x 1010 and 1 x 1011 s-1.
Author(s): Wright C, Sykes AG
Publication type: Article
Publication status: Published
Journal: Macromolecular Symposia
Year: 2000
Volume: 156
Issue: 1
Pages: 269-275
ISSN (print): 1022-1360
ISSN (electronic):
Publisher: Wiley - VCH Verlag GmbH & Co
URL: .htp://dx.doi.org/10.1002/1521-3900(200007)156:1<269::AID-MASY269>3.0.CO;2-7
DOI: 10.1002/1521-3900(200007)156:1<269::AID-MASY269>3.0.CO;2-7
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