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Proton NMR investigation of the electron-exchange reaction between hexaammineruthenium(II) and hexaammineruthenium(III) ions

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00233a033· OSTI ID:5659156
The rate of the electron-self-exchange reaction between (Ru(NH/sub 3/)/sub 6/)/sup 3 +/ and (Ru(NH/sub 3/)/sub 6/)/sup 2 +/ has been measured by proton NMR line broadening. The system is complicated by the equation of (Ru(NH/sub 3/)/sub 6/)/sup 2 +/, which results in reduction of the small amount of (Ru(NH/sub 3/)/sub 6/)/sup 3 +/ present. To reduce this difficulty, measurements were performed at 4/sup 0/C. Rate constants are (6.6 +/- 1.0) x 10/sup 3/ and (9.9 +/- 0.2) X 10/sup 3/ M/sup -1/ s/sup -1/ for solutions of 0.125 and 0.250 M (Ru(NH/sub 3/)/sub 6/)Cl/sub 2/, respectively. These rate constants are in order-of-magnitude agreement with those previously reported. The reaction appears to be catalyzed by chloride ion. A rate constant for the uncatalyzed reaction at 4/sup 0/C and an ionic strength approx.0.5 M is estimated to be 3.3 x 10/sup 3/ M/sup -1/ s/sup -1/. The activation enthalpy is about 5 kcal mol/sup -1/.
Research Organization:
Univ. of Sydney, Australia
OSTI ID:
5659156
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 25:13; ISSN INOCA
Country of Publication:
United States
Language:
English