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Kinetic studies of outer-sphere redox reactions of. mu. -pyrazinedecaaminediruthenium(II,II), -(II,III), and -(III,III)

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100407a041· OSTI ID:5458636
;

Rate constants for outer-sphere cross-reactions of the couples Ru/sub 2/(NH/sub 3/)/sub 10/pz/sup 6+/5+/ (pz = pyrazine), Ru/sub 2/(NH/sub 3/)/sub 10/pz/sup 5+/4+/, RuRh(NH/sub 3/)/sub 10/pz/sup 6+/5+/, Ru(NH/sub 3/)/sub 5/pz/sup 3+/2+/, and Ru(NH/sub 3/)/sub 5/pzCH/sub 3//sup 4+/3+/ (pzCH/sub 3/ = methylpyrazinium) with the couples Ru-(NH/sub 3/)/sub 5/py/sup 3+/2+/ (py = pyridine), Ru(NH/sub 3/)/sub 4/(bpy)/sup 3+/2+/ (bpy = 2,2'-bipyridine), and Co(bpy)/sub 3//sup 3+/2+/ have been measured at 25/sup 0/C and ionic strength 0.10 M (trifluoromethanesulfonate). The rate constants for the Ru(NH/sub 3/)/sub 5/py/sup 3+/2+/ and Ru-(NH/sub 3/)/sub 4/bpy/sup 3+/2+/ reactions were treated according to the electrostatically corrected, adiabatic Marcus equation and yielded the following estimates of the rate constants for self-exchange reactions (in the same order as above): 15, 6.7 x 10/sup 3/, 9.0, 1.4 x 10/sup 4/, and 39 M/sup -1/s/sup -1/. The trends are discussed on the basis of inner-sphere and outer-sphere reorganization energies. The cross-reactions of the Co(bpy)/sub 3//sup 3+/2+/ couple appear to be mildly nonadiabatic.

Research Organization:
State Univ. of New York, Stony Brook
OSTI ID:
5458636
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 90:16; ISSN JPCHA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
AMMINES
AZINES
BIPYRIDINES
CHEMICAL REACTION KINETICS
COBALT COMPLEXES
COMPLEXES
DATA
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
INFORMATION
KINETICS
MEDIUM TEMPERATURE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRAZINES
PYRIDINES
REACTION KINETICS
RHODIUM COMPLEXES
RUTHENIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES