Functional groups electronic effects

Tab. 5.3 Inductive and Resonance Substituent Effects of Various Functional Groups Electron donation...

BF3-Et20, NaCNBHs, THF, reflux 4-24 h, 65-98% yield. Functional groups such aryl ketones and nitro compounds are reduced and electron-rich phenols tend to be alkylated with the released benzyl carbenium ion. The use of BF3 Et20 and triethylsilane as a cation scavenger is also effective." ... 

Silyl ethers are among the most frequently used protective groups for the alcohol function. This stems largely from the fact that their reactivity (both formation and cleavage) can be modulated by a suitable choice of substituents on the silicon atom. Both steric and electronic effects are the basic controlling elements that regulate the ease of cleavage in multiply functionalized substrates. In plan-... 

Since the electrostatic potential sharply decreases with increasing distance from the polyelectrolyte cylinder, the degree of reactivity modification by functional groups fixed to the polyion is strongly dependent on the distance from the cylinder surface. Considerable electrostatic potential effects on the photoinduced forward and thermal back electron transfer reactions, which will be discussed in the following chapters, can be attributed to the functional chromophore groups directly attached to the polyelectrolyte back-bone through covalent bonds. 

Several mechanisms have been proposed to explain the activation of carbon surfaces. These have Included the removal of surface contaminants that hinder electron transfer, an Increase In surface area due to ralcro-roughenlng or bulld-up of a thin porous layer, and an Increase In the concentrations of surface functional groups that mediate electron transfer. Electrode deactivation has been correlated with an unintentional Introduction of surface contaminants (15). Improved electrode responses have been observed to follow treatments which Increase the concentration of carbon-oxygen functional groups on the surface (7-8,16). In some cases, the latter were correlated with the presence of electrochemical surface waves (16-17). However, none of the above reports discuss other possible mechanisms of activation which could be responsible for the effects observed. 

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