Single-electron transfer mechanism

The equation does not take into account such pertubation factors as steric effects, solvent effects, and ion-pair formation. These factors, however, may be neglected when experiments are carried out in the same solvent at the same temperature and concentration for an homogeneous set of substrates. So, for a given ambident nucleophile the rate ratio kj/kj will depend on A and B, which vary with (a) the attacked electrophilic center, (b) the solvent, and (c) the counterpart cationic species of the anion. The important point in this kind of study is to change only one parameter at a time. This simple rule has not always been followed, and little systematic work has been done in this field (12) stiH widely open after the discovery of the role played by single electron transfer mechanism in ambident reactivity (1689). 

Mechanistic studies on the formation of PPS from polymerization of copper(I) 4-bromobenzenethiolate in quinoline under inert atmosphere at 200°C have been pubUshed (91). PPS synthesized by this synthetic procedure is characterized by high molar mass at low conversions and esr signals consistent with a single-electron-transfer mechanism, the Sj l-type mechanism described earlier (22). 

It has been proposed that there may be a single electron transfer mechanism for the Mukaiyama reaction under certain conditions.72 For example, photolysis of benzaldehyde dimethylacetal and 1-trimethylsilyloxycyclohexene in the presence of a... 

In contrast to [L Pd], oxidative addition of aryl halides on [L Ni] often proceed by single electron transfer mechanism [2, 197]. SN2 and SNAr types of oxidative addition as a step of the catalytic dehalogenation have also been proposed in the literature for low-valent Ti [40, 114], Zr(II) [115], Ru(II) [20, 74, 81, 98],... 

These alkylations can be looked upon as aliphatic nucleophilic substitutions, usually thoughtto proceed via SnI, Sn2, or hybrids of these mechanisms. However, in recent years more and more evidence for a single-electron transfer (SET) mechanism, represented in Eqs. (28-31), was obtained, and it was suggested that Sn2 and SET are just limiting cases of the same single-electron transfer mechanism [205, 206]. The S ET pathway involves first a transfer of an electron from the nucleophile to the electrophile followed by bond formation, whereas the Sn2 reaction involves a... 

The oxidation of alkyl aryl sulfides to sulfoxides with oxochromium(V) complexes is first order in oxidant and in substrate. The better correlation of log k with a+ rather than a and the low magnitude of p+ value (-1.19) were interpreted as evidence for a rate-determining single-electron-transfer mechanism. This was further supported by good correlation in the plots of log k versus oxidation potential/ionization energy. 

Mechanisms that begin this way are called SET (single electron transfer) mechanisms 59 Once formed, the radical ion cleaves ... 

These reactions occur easily because of the relative stability of the radicals involved.6 The single electron transfer mechanism (SET), which we have met several times (e.g., p. 307) is an important case. 

While the reaction is generally thought to proceed through a nucleophilic addition mechanism, sterically hindered substrates may react according to mi SET (single electron transfer) mechanism ... 

The involvement of styryl as a diene partner has also been demonstrated in the photosensitized electron transfer [4 + 2] intramolecular cycloaddition of l,l,8,8-tetraphenyl-l-7-octadiene (Scheme 9.29) [43]. This reaction is promoted by 1,4-dicyanobencene (DCB), and a single electron-transfer mechanism has been suggested. 

The role of the silver salt is not completely understood. No evidence for a single electron transfer mechanism has been found. Although extremely reactive electrophilic fluorinating agents, such as xenon fluoride triflate (FXeOTf) or trifluoromcthanesulfonyloxy fluoride (TfOF), may be generated from the combination of xenon difluoride and silver(l) triflate, the reaction appears to proceed following initial interaction of the alkcnc with the silver ion. ... 

Protium/deuterium/tritium kinetic isotope effects are often used to support hydride transfer mechanisms over single electron transfer mechanisms. However, sequential electron/proton/electron transfer mechanisms can easily show isotope effects as well. Even though the rate limiting step in the overall two electron reduction of flavin or NADH may be the isotope independent endergonic electron tunneling to form a radical intermediate state, once formed, this radical state can return the electron to recreate the... 

The SET (single electron transfer) mechanism can be invoked in the transannular addition of secondary amines to 1,1-diarylalkcncs in the presence of a catalytic amount of butyllithium, sodium naphthalenide or potassium hydroxide52, since the regiochemistry which is observed is opposite to that predicted by assuming the formation of metal amides. 

---