Electron transfer, activation control

We have proposed the concept of electroauxiliary,10 which activates substrate molecules toward electron transfer and controls a reaction pathway that would favor the formation of the desired products. For example, preintroduction of an electroauxiliary such as a silyl group to a carbon a to nitrogen gives rise to selective introduction of a nucleophile on the carbon to which the auxiliary has been attached. The use of a silyl group as electroauxiliary was... 

Steric Control of the Inner/Outer-Sphere Electron Transfer 461 Thermal and Photochemical ET in Strongly Coupled CT Complexes 463 Electron-Transfer Paradigm for Arene Transformation via CT Complexes 465 Electron-Transfer Activation of Electrophilic Aromatic Substitution 469 Structural Pre-organization of the Reactants in CT Complexes 470 CT Complexes in Aromatic Nitration and Nitrosation 472 Concluding Summary 475 References 475... 

Pai et al. (1983) measured hole mobilities of a series of bis(diethylamino)-substituted triphenylmethane derivatives doped into a PC and poly(styrene) (PS). The mobilities varied by four orders of magnitude, while the field dependencies varied from linear to quadratic. In all materials, the field dependencies decreased with increasing temperature. The temperature dependencies were described by an Arrhenius relationship with activation energies that decrease with increasing field. Pai et al. described the transport process as a field-driven chain of oxidation-reduction reactions in which the rate of electron transfer is controlled by the molecular substituents of the hopping sites. 

Substituents on the hydroquinone with lone pairs enhance the binding (Table 5) and allow bidentate co-ordination of the hydroquinone. It is proposed that the phenolate oxygen is co-ordinated by type 2 copper whereas the lone-pair substituent is associated with the type 3 dinuclear reduction centre. Binding is also affected by bulky substituents and by the distance between the two co-ordinating groups. Electron transfer is controlled by protein activation rather than by the ease of activation of the hydroquinones. 

Modem electron transfer tlieory has its conceptual origins in activated complex tlieory, and in tlieories of nonradiative decay. The analysis by Marcus in tire 1950s provided quantitative connections between the solvent characteristics and tire key parameters controlling tire rate of ET. The Marcus tlieory predicts an adiabatic bimolecular ET rate as... 

An air valve, sometimes called the air-activated valve, is widely used for automated food handling operations. Although electronic or electric control boxes may be a part of the system, the valve itself generally is air-activated, and is more reflable than other types. Air-operated valves are used for in-place cleaning systems, and for the transfer and flow control of various products. 

In deriving the kinetics of activation-energy controlled charge transfer it was emphasised that a simple one-step electron-transfer process would be considered to eliminate the complications that arise in multistep reactions. The h.e.r. in acid solutions can be represented by the overall equation ... 

The electron transfer from a methanol molecule to the activated diazonium ion is obviously a diffusion-controlled reaction. The rate constant is of the same order... 

PBE dendrons bearing a focal bipyridine moiety have been demonstrated to coordinate to Ru + cations, exhibiting luminescence from the metal cation core by the excitation of the dendron subunits [28-30]. The terminal peripheral unit was examined (e.g., phenyl, naphthyl, 4-f-butylphenyl) to control the luminescence. The Ru +-cored dendrimer complexes are thought to be photo/redox-active, and photophysical properties, electrochemical behavior, and excited-state electron-transfer reactions are reported. 

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