Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

Carbon-13 NMR investigation of the electron exchange reaction between tris(ethylenediamine)ruthenium(II) and tris(ethylenediamine)ruthenium(III) ions

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100407a040· OSTI ID:5331878
The rate of electron exchange between Ru(en)/sub 3//sup 3 +/ and Ru(en)/sub 3//sup 2 +/ has been measured by NMR line-broadening techniques observing the /sup 13/C spectrum of the diamagnetic Ru(II) complex. At 298 K in a solution of 0.25 M (Ru(en)/sub 3/)(CF/sub 3/SO/sub 3/)/sub 2/, giving an ionic strength of 0.75 M, the rate constant is 3.1 x 10/sup 4/ M/sup -1/s/sup -1/, with ..delta..H/sup */ = 6.0 kcal mol/sup -1/ and ..delta..S/sup */ = -17 cal deg/sup -1/ mol/sup -1/. At half this concentration of Ru(II) the rate constant is 1.7 x 10/sup 4/ M/sup -1/s/sup -1/. These rates are more rapid than the corresponding Ru(NH/sub 3/)/sub 6//sup 3+/2+/ electron exchange rate, as is predicted by the Marcus theory of electron transfer.
Research Organization:
Univ. of Sydney, Australia
OSTI ID:
5331878
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