Time-Resolved Kinetic Study of the Electron-Transfer Reactions between Ring-Substituted Cumyloxyl Radicals and Alkylferrocenes. Evidence for an Inner-Sphere Mechanism

2011 ◽  
Vol 76 (6) ◽  
pp. 1789-1794 ◽  
Author(s):  
Massimo Bietti ◽  
Gino A. DiLabio ◽  
Osvaldo Lanzalunga ◽  
Michela Salamone
Keyword(s):  
Electron Transfer ◽  
Kinetic Study ◽  
Transfer Reactions ◽  
Time Resolved ◽  
Electron Transfer Reactions ◽  
Inner Sphere ◽  
Sphere Mechanism

Electron-transfer reactions in non-aqueous media. VII. Reduction of CoF(NH3)52+ and Co(HCOO)(NH3)52+ by copper(I) in dimethyl sulfoxide-water mixtures

1983 ◽  
Vol 36 (10) ◽  
pp. 1923 ◽  
Author(s):  
JMB Harrowfield ◽  
L Spiccia ◽  
DW Watts
Keyword(s):  
Electron Transfer ◽  
Dimethyl Sulfoxide ◽  
Aqueous Media ◽  
Mixed Solvents ◽  
Transfer Reactions ◽  
Aprotic Solvents ◽  
Aqueous Mixtures ◽  
Electron Transfer Reactions ◽  
Dipolar Aprotic Solvents ◽  
Sphere Mechanism

Previous work on the reduction of a series of cobalt(III) complexes by iron(II) in dipolar aprotic solvents and in aqueous mixtures has been extended to reduction by copper(I). The greater stability of copper(I) to disproportionation in these media has permitted the study of the reduction of CoF(NH3)52+ and Co(HCOO)(NH3)52+ in range of solvents over a number of temperatures with a precision not possible in previous studies in water. The results are consistent with an inner-sphere mechanism in which the copper(I) reductant is preferentially solvated by dimethyl sulfoxide to the exclusion of water in mixed solvents.

Single vs double bridging in inner-sphere electron transfer reactions

Polyhedron ◽  
1992 ◽  
Vol 11 (5) ◽  
pp. 517-521 ◽  
Author(s):  
Soontaree Benjarvongkulchai ◽  
Roderick D. Cannon
Keyword(s):  
Electron Transfer ◽  
Transfer Reactions ◽  
Electron Transfer Reactions ◽  
Inner Sphere

Quantum theory of inner sphere electron transfer reactions

1970 ◽  
Vol 23 (7) ◽  
pp. 1287 ◽  
Author(s):  
PP Schmidt
Keyword(s):  
Electron Transfer ◽  
Transition State ◽  
Bond Formation ◽  
Transfer Reactions ◽  
Reaction Sequence ◽  
Electron Transfer Reactions ◽  
Bond Forming ◽  
Inner Sphere ◽  
Franck Condon ◽  
Activated Complex

This paper reports a theory of inner sphere electron transfer reactions for which, in addition to the electron transfer, there is bond formation and/or destruction. We assume that steps in the reaction sequence which involve bond synthesis take place in intermediate activated complex states. The problem of inner sphere electron transfer is large and complicated. The theory described applies to one aspect of the problem, namely, the dynamics of simultaneous electron transfer and bond break in the transition state complex. However, we assume the intermediate complex exists in steady state equilibrium with the reactants. The theory developed in this paper reveals features important in the unimolecular decay of the transition state. In particular, the importance of the Franck-Condon restrictions on bond forming and breaking steps is demonstrated.

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