Gated Electron Transfer
Living reference work entry
Gated electron transfer is a process in which a relatively slow nonelectron transfer reaction is required to activate the system for a much faster true electron transfer reaction.
Gated electron transfer occurs when a relatively slow adiabatic (nonelectron transfer) reaction precedes a faster nonadiabatic (true electron transfer) reaction, and the slower reaction is required to activate the system for electron transfer. If the rates of these two sequential reactions cannot be kinetically distinguished, then the observed rate constant ( k obs) for the redox reaction will not be the true electron transfer rate constant ( k ET). Instead it will be the rate constant for the preceding slower reaction step. Gated electron transfer could occur in a bimolecular electron transfer reaction in which some rearrangement of reactants must occur after initial binding to optimize the system for electron transfer (Eq. 1), or it could occur during...
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