Mechanism of Inner-Sphere Electron Transfer via Charge-Transfer (Precursor) Complexes. Redox Energetics of Aromatic Donors with the Nitrosonium Acceptor

2001 ◽  
Vol 123 (37) ◽  
pp. 8985-8999 ◽  
Author(s):  
Sergiy V. Rosokha ◽  
Jay K. Kochi
Keyword(s):  
Electron Transfer ◽  
Charge Transfer ◽  
Inner Sphere

Zur Theorie der Elektronenübergangsreaktionen in molekularen Komplexen / Theory of Electron Transfer Reactions in Molecular Complexes

1974 ◽  
Vol 29 (6) ◽  
pp. 880-887 ◽  
Author(s):  
P. P. Schmidt
Keyword(s):  
Activation Energy ◽  
Electron Transfer ◽  
Charge Transfer ◽  
Rate Constant ◽  
Reaction Rate ◽  
Charge Transfer Complex ◽  
Rate Theory ◽  
Transfer Step ◽  
Donor And Acceptor ◽  
Inner Sphere

This paper reports a theory of the inner sphere-type electron transfer reaction. Inner sphere reactions, as opposed to the outer sphere variety, require that the solvate or ligand shells surrounding the electron donor and acceptor species undergo considerable change in the course of the electron transfer. In this paper we assume that the electron transfer step takes place in a molecular complex which exists in equilibrium with the reactants. The electron transfer step occurs as a non-radiative charge transfer-type transition. In this manner we treat the charge transfer kinetics, in particular, the evaluation of the reaction rate constant, in the same manner as is usual for non-radiative problems. The analysis leading to the rate constant expression is based on Yamamoto’s general chemical reaction rate theory. The rate constant expressions obtained are quite general, they hold for any degree of strength of coupling between subsystems comprising the entire system. The activation energy, in the Arrhenius form for the rate constant, shows a dependence on the energy (work) of formation of the intermediate charge transfer complex, on vibrational shift energies associated with the molecular motions of the ligands, and on solvent repolarization energies. The activation energy also shows an important dependence on coupling terms which link the vibrations of the molecular inner shell with the polarization states of the (assumed) dielectric continuum which surrounds the charge transfer participants. The approach we take in developing this theory we believe points the way towards the development of a more complete theory capable of accounting for the dynamics of the molecular reorganization leading to the intermediate charge transfer complex as well as accounting for the electron transfer step itself.

From charge transfer to electron transfer in halogen-bonded complexes of electrophilic bromocarbons with halide anions

2015 ◽  
Vol 17 (7) ◽  
pp. 4989-4999 ◽  
Author(s):  
Sergiy V. Rosokha ◽  
Alfredo Traversa
Keyword(s):  
Electron Transfer ◽  
Charge Transfer ◽  
Halogen Bonding ◽  
Dramatic Decrease ◽  
Halide Anions ◽  
Inner Sphere ◽  
Bonded Complexes

Halogen bonding leads to a dramatic decrease of the barrier for (inner-sphere) electron transfer and halogen transfer between bromocarbons and iodide anions.

Optimized Electron Transfer in Charge-Transfer Ion Pairs. Pronounced Inner-Sphere Behavior of Olefin Donors

1996 ◽  
Vol 118 (16) ◽  
pp. 3842-3851 ◽  
Author(s):  
Stephan M. Hubig ◽  
T. Michael Bockman ◽  
Jay K. Kochi
Keyword(s):  
Electron Transfer ◽  
Charge Transfer ◽  
Ion Pairs ◽  
Inner Sphere

scholarly journals RuIII(edta) complexes as molecular redox catalysts in chemical and electrochemical reduction of dioxygen and hydrogen peroxide: inner-sphere versus outer-sphere mechanism

RSC Advances ◽  
2021 ◽  
Vol 11 (35) ◽  
pp. 21359-21366
Author(s):  
Debabrata Chatterjee ◽  
Marta Chrzanowska ◽  
Anna Katafias ◽  
Maria Oszajca ◽  
Rudi van Eldik
Keyword(s):  
Hydrogen Peroxide ◽  
Electron Transfer ◽  
Electrochemical Reduction ◽  
Molecular Oxygen ◽  
Outer Sphere ◽  
Transfer Processes ◽  
Edta Complexes ◽  
Inner Sphere ◽  
Electron Transfer Processes ◽  
Sphere Mechanism

[RuII(edta)(L)]2–, where edta4– =ethylenediaminetetraacetate; L = pyrazine (pz) and H2O, can reduce molecular oxygen sequentially to hydrogen peroxide and further to water by involving both outer-sphere and inner-sphere electron transfer processes.

The dehydrogenation of 1,4-dihydronaphthalene by tetrachloro-p-benzoquinone

1976 ◽  
Vol 54 (14) ◽  
pp. 2261-2265 ◽  
Author(s):  
Z. M. Hashish ◽  
I. M. Hoodless
Keyword(s):  
Electron Transfer ◽  
Charge Transfer ◽  
Reaction Rate ◽  
Second Order ◽  
Charge Transfer Complexes ◽  
Ion Transfer ◽  
Hydride Ion ◽  
Rate Determining Step ◽  
Hydride Ion Transfer

The dehydrogenation of 1,4-dihydronaphthalene by tetrachloro-p-benzoquinone in phenetole solution has been investigated. The present work does not fully confirm earlier studies which report that the reaction follows second-order kinetics and that the hydride ion transfer is rate determining. In the investigations described in this paper second-order kinetics are only observed in the later stages of the reaction and a 1:1 stoichiometry of the reactants in the process is not obtained. Substitution of tritium in the 1,4-positions of the hydrocarbon appears to not significantly affect the reaction rate. The present results indicate that charge-transfer complexes are formed in the reaction and it is suggested that electron transfer within these complexes could be the rate-determining step in the dehydrogenation.

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