Abstract
One limiting mechanism proposed for bridged inner-sphere, electron transfer reactions, the chemical mechanism, involves rate-limiting reduction of the bridge to a radical by the reducing centre followed by rapid reduction of the oxidizing centre by the radical bridge. One predicted kinetic trait of such reactions is a correlation between the electron transfer rate constant and the "reducibility" of the bridge. This predicted trend is quantified here for the first time, with bridge reducibility expressed in terms of adiabatic gas-phase electron affinities. Also, a new kinetic test to distinguish outer-sphere electron transfers from those proceeding the chemical mechanism is shown to develop from the dependence of the rate constant on electron affinity.
| Original language | English |
|---|---|
| Pages (from-to) | 563-565 |
| Number of pages | 3 |
| Journal | Polyhedron |
| Volume | 8 |
| Issue number | 4 |
| DOIs | |
| State | Published - Jan 1 1989 |
Fingerprint
ASJC Scopus subject areas
- Biochemistry
- Inorganic Chemistry
- Physical and Theoretical Chemistry
- Materials Chemistry
Cite this
The chemical mechanism for electron transfer and bridge reducibility. / Purcell, William L.
In: Polyhedron, Vol. 8, No. 4, 01.01.1989, p. 563-565.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - The chemical mechanism for electron transfer and bridge reducibility
AU - Purcell, William L.
PY - 1989/1/1
Y1 - 1989/1/1
N2 - One limiting mechanism proposed for bridged inner-sphere, electron transfer reactions, the chemical mechanism, involves rate-limiting reduction of the bridge to a radical by the reducing centre followed by rapid reduction of the oxidizing centre by the radical bridge. One predicted kinetic trait of such reactions is a correlation between the electron transfer rate constant and the "reducibility" of the bridge. This predicted trend is quantified here for the first time, with bridge reducibility expressed in terms of adiabatic gas-phase electron affinities. Also, a new kinetic test to distinguish outer-sphere electron transfers from those proceeding the chemical mechanism is shown to develop from the dependence of the rate constant on electron affinity.
AB - One limiting mechanism proposed for bridged inner-sphere, electron transfer reactions, the chemical mechanism, involves rate-limiting reduction of the bridge to a radical by the reducing centre followed by rapid reduction of the oxidizing centre by the radical bridge. One predicted kinetic trait of such reactions is a correlation between the electron transfer rate constant and the "reducibility" of the bridge. This predicted trend is quantified here for the first time, with bridge reducibility expressed in terms of adiabatic gas-phase electron affinities. Also, a new kinetic test to distinguish outer-sphere electron transfers from those proceeding the chemical mechanism is shown to develop from the dependence of the rate constant on electron affinity.
UR - http://www.scopus.com/inward/record.url?scp=45249125541&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=45249125541&partnerID=8YFLogxK
U2 - 10.1016/S0277-5387(00)80761-5
DO - 10.1016/S0277-5387(00)80761-5
M3 - Article
AN - SCOPUS:45249125541
VL - 8
SP - 563
EP - 565
JO - Polyhedron
JF - Polyhedron
SN - 0277-5387
IS - 4
ER -