Electron rates, intramolecular

In Debye solvents, x is tire longitudinal relaxation time. The prediction tliat solvent polarization dynamics would limit intramolecular electron transfer rates was stated tlieoretically [40] and observed experimentally [41]. 

Kosower E M and Huppert D 1983 Solvent motion controls the rate of intramolecular electron transfer Chem. Phys. Lett. 96 433-5... 

This considerable enhancement in redox properties may however remain chemically hidden. Several causes may converge to mask these properties. First of all electron transfer is an intermolecular act of reactivity even when thermodynamically feasible it may have to compete with very rapid intramolecular acts of deactivation (fluorescence, phosphorescence, internal conversion)99. The rate of electron transfer is given by the Rehm-Weller equation96,100... 

The interconversion between different spin states is closely related to the intersystem crossing process in excited states of transition-metal complexes. Hence, much of the interest in the rates of spin-state transitions arises from their relevance to a better understanding of intersystem crossing phenomena. The spin-state change can alternatively be described as an intramolecular electron transfer reaction [34], Therefore, rates of spin-state transitions may be employed to assess the effect of spin multiplicity changes on electron transfer rates. These aspects have been covered in some detail elsewhere [30]. 

The rate of degenerate intramolecular electron-transfer processes in biselectrophoric redox systems, and the observed spin-density distribution over one or two units depend upon the overall reorganization energy and thus upon... 

In this mechanism, the rate-determining step is the intramolecular electron transfer from the ligand to dioxygen, Eq. (18), via the metal center of the [M(HA)(02)] 1 + complex for which the following structure was proposed ... 

Using a typical A value for intramolecular electron transfer of 750 mV, it is possible to use the Dutton s ruler expression to determine the rates of the two electron-transfer processes ... 

In this equation g(r) is the equilibrium radial distribution function for a pair of reactants (14), g(r)4irr2dr is the probability that the centers of the pair of reactants are separated by a distance between r and r + dr, and (r) is the (first-order) rate constant for electron transfer at the separation distance r. Intramolecular electron transfer reactions involving "floppy" bridging groups can, of course, also occur over a range of separation distances in this case a different normalizing factor is used. 

Intramolecular Electron-Transfer Rates. Experiments were carried out under inert atmosphere by reducing a known concen-... 

Influence of the Amino Acid Linkages on Intramolecular Electron-Transfer Rates. There is a significant drop in the 2... 

It is too early to draw any conclusions about the insensitivity of the rate constants to the nature of the dipeptide. Differences among the peptides seem to be revealed more in the temperature dependencies of the rate constants for intramolecular electron transfer than in the magnitude of the rate constant itself. Work is in progress on the synthesis of other di-, tri-, and tetra-peptides separating Co(III) and Ru(II) in order to examine the temperature dependence of the intramolecular rate... 

Table I. Intramolecular Electron Transfer Rates and Activation Parameters ...

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