Marcus Theory: Thermodynamics CAN Control the Kinetics of Electron Transfer Reactions

2012 ◽  
Vol 89 (9) ◽  
pp. 1159-1167 ◽  
Author(s):  
Todd P. Silverstein
Keyword(s):  
Electron Transfer ◽  
Marcus Theory ◽  
Transfer Reactions ◽  
Electron Transfer Reactions ◽  
Kinetics Of

Kinetics of electron-transfer reactions of the Co(bpyO2)32+/3+ couple in acetonitrile

1992 ◽  
Vol 70 (1) ◽  
pp. 39-45 ◽  
Author(s):  
Donal H. Macartney ◽  
Samuel Mak
Keyword(s):  
Electron Transfer ◽  
Exchange Rate ◽  
Rate Constants ◽  
Marcus Theory ◽  
Transfer Reactions ◽  
Electron Transfer Reactions ◽  
Cross Reactions ◽  
The Cross ◽  
Polypyridine Complexes ◽  
Kinetics Of

The kinetics of the outer-sphere electron transfer reactions of tris(1,1′-dioxo-2,2′-bipyridine)cobalt(II) and (III) with a series of nickel polyaza macrocycles, FeL3n+ and OsL32+ complexes (L is 2,2′-bipyridine or 1,10-phenanthroline, and substituted derivatives), and Rh2(O2CCH3)4(CH3CN)2+ have been investigated in acetonitrile at 25.0 °C. An application of the Marcus theory relationship to the cross-reaction rate constants yielded apparent Co(bpyO2)32+/3+ self-exchange rate constants of 102 M−1 s−1 from the nickel macrocycle cross-reactions and 10−1 M−1 s−1 from the cross-reactions with the metal polypyridine complexes. The latter cross-reactions are considered to be non-adiabatic due to a mismatch in the donor/acceptor orbital symmetries. The electron exchange rate constant is compared with the exchange rate constants for other Co(II)/Co(III) complex couples and M(bpyO2)32+/3+ couples of other first-row transition metals, and discussed in terms of inner-sphere and solvent reorganization barriers. Keywords: electron transfer, Marcus theory relationship, cobalt(II)/(III) couples, 1,1′-dioxo-2,2′-bipyridine.

Kinetics of intra-polymer electron-transfer reactions in macromolecule–metal complexes

1995 ◽  
Vol 91 (17) ◽  
pp. 2877-2880 ◽  
Author(s):  
Masahiro Suzuki ◽  
Satoshi Kobayashi ◽  
Toshiki Koyama ◽  
Kenji Hanabusa ◽  
Hirofusa Shirai ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Metal Complexes ◽  
Transfer Reactions ◽  
Electron Transfer Reactions ◽  
Kinetics Of
Sign in / Sign up

Export Citation Format

Share Document