Gas-phase electron transfer: direct observation of kinetic barriers in metallocene self-exchange reactions

1985 ◽  
Vol 107 (21) ◽  
pp. 6130-6131 ◽  
Author(s):  
John R. Eyler ◽  
David E. Richardson
Keyword(s):  
Electron Transfer ◽  
Gas Phase ◽  
Direct Observation ◽  
Exchange Reactions ◽  
Kinetic Barriers

THEORETICAL STUDIES ON THE COUPLING INTERACTIONS AND SELF-EXCHANGE REACTION MECHANISMS IN THE COMPLEXES OF NO WITH ONH AND NOH

2008 ◽  
Vol 07 (03) ◽  
pp. 435-446 ◽  
Author(s):  
PING LI ◽  
XIAOYAN XIE ◽  
YUXIANG BU ◽  
WEIHUA WANG ◽  
NANA WANG ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Exchange Reaction ◽  
Reaction Mechanisms ◽  
Natural Bond Orbital ◽  
Theoretical Studies ◽  
Exchange Reactions ◽  
Electron Transfer Mechanism ◽  
Proton Coupled Electron Transfer ◽  
Planar Geometries ◽  
Transfer Mechanisms

The coupling interactions and self-exchange reaction mechanisms between NO and ONH (NOH) have been systematically investigated at the B3LYP/6-311++G** level of theory. All the equilibrium complexes are characterized by the intermolecular H-bonds and co-planar geometries. The cisoid NOH/ON species is the most stable one among all the complexes considered due to the formation of an N – N bond. Moreover, all the cisoid complexes are found to be more stable than the corresponding transoid ones. The origin of the blueshifts occurring in the selected complexes has been explored, employing the natural bond orbital (NBO) calculations. Additionally, the proton transfer mechanisms for the self-exchange reactions have been proposed, i.e. they can proceed via the three-center proton-coupled electron transfer or five-center cyclic proton-coupled electron transfer mechanism.

Electron Transfer and Ligand Addition to Atomic Mercury Cations in the Gas Phase:  Kinetic and Equilibrium Studies at 295 K

2006 ◽  
Vol 45 (24) ◽  
pp. 9646-9653 ◽  
Author(s):  
Xiang Zhao ◽  
Eric Flaim ◽  
Lise Huynh ◽  
Michael J. Y. Jarvis ◽  
Ping Cheng ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Gas Phase ◽  
Equilibrium Studies ◽  
Ligand Addition ◽  
Atomic Mercury

Volumes of activation for electrode processes of various charge-types in nonaqueous solvents

2001 ◽  
Vol 79 (12) ◽  
pp. 1864-1869 ◽  
Author(s):  
Mitsuru Matsumoto ◽  
Delanie Lamprecht ◽  
Michael R North ◽  
Thomas W Swaddle
Keyword(s):  
Electron Transfer ◽  
Reaction Rate ◽  
Electrode Reaction ◽  
State Theory ◽  
Exchange Reactions ◽  
Pt Electrode ◽  
Electrode Processes ◽  
Solvent Dynamics ◽  
The Mean ◽  
Dynamical Control

Volumes of activation (ΔV‡el) are reported for electron transfer at a Pt electrode of Mn(CN-cyclo-C6H11)62+/+ in acetonitrile, acetone, methanol, and propylene carbonate, and of Fe(phen)33+/2+ in acetonitrile. In all cases, ΔV‡el is markedly positive, whereas for the homogeneous self-exchange reactions of these couples in the same solvents the corresponding parameter is known to be strongly negative. The rate constants for the electrode reactions correlate loosely with the mean reactant diffusion coefficients (i.e., with solvent fluidity) and the ΔV‡el values with the volumes of activation for diffusion (i.e., for viscous flow), consistent with solvent dynamical control of the electrode reaction rate in organic solvents. A detailed analysis of ΔV‡el values of the kind presented for a couple with an uncharged member (Zhou and Swaddle, Can. J. Chem. 79, 841 (2001)) fails, however, either because of ion-pairing effects with these more highly charged couples or because of breakdown of transition-state theory in predicting the contribution of the activational barrier. Attempts to measure ΔV‡el for the oxidation of the uncharged molecule ferrocene at various electrodes in acetonitrile were unsuccessful, although ΔV‡el was again seen to be clearly positive.Key words: electrode kinetics, volumes of activation, nonaqueous electron transfer, solvent dynamics.

Direct Observation of an Intermediate State for a Surface Photochemical Reaction Initiated by Hot Electron Transfer

2005 ◽  
Vol 109 (30) ◽  
pp. 14481-14485 ◽  
Author(s):  
Junseok Lee ◽  
Sunmin Ryu ◽  
Jinyoung Chang ◽  
Sangjin Kim ◽  
Seong Keun Kim
Keyword(s):  
Electron Transfer ◽  
Direct Observation ◽  
Intermediate State ◽  
Photochemical Reaction ◽  
Hot Electron ◽  
Hot Electron Transfer
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