Electron transfer successive processes

Reductive Cross-Coupling of Nitrones Recently, reductive coupling of nitrones with various cyclic and acyclic ketones has been carried out electrochem-ically with a tin electrode in 2-propanol (527-529). The reaction mechanism is supposed to include the initial formation of a ketyl radical anion (294), resulting from a single electron transfer (SET) process, with its successive addition to the C=N nitrone bond (Scheme 2.112) (Table 2.9). 

Monomer 61 has a very large steric demand and it is subject to the same internal electron-transfer/termination process discovered earlier for vinylferrocene polymerizations. Only modest molecular weights were achieved and reinitiation sequences were required to get, in our hands, a 31% maximum yield. Copolymerizations with styrene were also successfully performed.90,91... 

Although it is conceptually useful to think of two successive processes following the initial ionization to A, the electron transfer and the generation of the Auger electron occur simultaneously. 

The reactivities of the substrate and the nucleophilic reagent change vyhen fluorine atoms are introduced into their structures This perturbation becomes more impor tant when the number of atoms of this element increases A striking example is the reactivity of alkyl halides S l and mechanisms operate when few fluorine atoms are incorporated in the aliphatic chain, but perfluoroalkyl halides are usually resistant to these classical processes However, formal substitution at carbon can arise from other mecharasms For example nucleophilic attack at chlorine, bromine, or iodine (halogenophilic reaction, occurring either by a direct electron-pair transfer or by two successive one-electron transfers) gives carbanions These intermediates can then decompose to carbenes or olefins, which react further (see equations 15 and 47) Single-electron transfer (SET) from the nucleophile to the halide can produce intermediate radicals that react by an SrnI process (see equation 57) When these chain mechanisms can occur, they allow reactions that were previously unknown Perfluoroalkylation, which used to be very rare, can now be accomplished by new methods (see for example equations 48-56, 65-70, 79, 107-108, 110, 113-135, 138-141, and 145-146)... 

Many anodic oxidations involve an ECE pathway. For example, the neurotransmitter epinephrine can be oxidized to its quinone, which proceeds via cyclization to leukoadrenochrome. The latter can rapidly undergo electron transfer to form adrenochrome (5). The electrochemical oxidation of aniline is another classical example of an ECE pathway (6). The cation radical thus formed rapidly undergoes a dimerization reaction to yield an easily oxidized p-aminodiphenylamine product. Another example (of industrial relevance) is the reductive coupling of activated olefins to yield a radical anion, which reacts with the parent olefin to give a reducible dimer (7). If the chemical step is very fast (in comparison to the electron-transfer process), the system will behave as an EE mechanism (of two successive charge-transfer steps). Table 2-1 summarizes common electrochemical mechanisms involving coupled chemical reactions. Powerful cyclic voltammetric computational simulators, exploring the behavior of virtually any user-specific mechanism, have... 

The cleavage mechanism can be clarified by cyclic voltammetries as shown in Figure 5. In aprotic solution (curves a) steps (l) and (2) correspond to the successive electron transfers leading finally to the dianion. On the other hand, in protic solution (curve c), step (2) has disappeared while step (l) has grown and then obviously corresponds to an ECE process. Anyhow, and whatever the medium, step (3) is identified as that in which the produced olefin (here 1,1-diphenylethylene) is reduced in all cases. 

This oxidative process has been successful with ketones,244 esters,245 and lactones.246 Hydrogen peroxide can also be used as the oxidant, in which case the alcohol is formed directly.247 The mechanisms for the oxidation of enolates by oxygen is a radical chain autoxidation in which the propagation step involves electron transfer from the carbanion to a hydroperoxy radical.248... 

P. Mitchell (Nobel Prize for Chemistry, 1978) explained these facts by his chemiosmotic theory. This theory is based on the ordering of successive oxidation processes into reaction sequences called loops. Each loop consists of two basic processes, one of which is oriented in the direction away from the matrix surface of the internal membrane into the intracristal space and connected with the transfer of electrons together with protons. The second process is oriented in the opposite direction and is connected with the transfer of electrons alone. Figure 6.27 depicts the first Mitchell loop, whose first step involves reduction of NAD+ (the oxidized form of nicotinamide adenosine dinucleotide) by the carbonaceous substrate, SH2. In this process, two electrons and two protons are transferred from the matrix space. The protons are accumulated in the intracristal space, while electrons are transferred in the opposite direction by the reduction of the oxidized form of the Fe-S protein. This reduces a further component of the electron transport chain on the matrix side of the membrane and the process is repeated. The final process is the reduction of molecular oxygen with the reduced form of cytochrome oxidase. It would appear that this reaction sequence includes not only loops but also a proton pump, i.e. an enzymatic system that can employ the energy of the redox step in the electron transfer chain for translocation of protons from the matrix space into the intracristal space. 

Complexes with pyridine-2,6-diimine ligands, five-coordinate [NiX2(174)] (X = C1, Br) or six-coordinate [Ni(174)2]X2, were usually assumed to have innocent neutral ligands. The X-ray structure and spectroscopic characteristics of [Ni(174)2](PF6) confirm that the complex contains the neutral ligand ([174] ) and a divalent nickel ion.579 The cyclic voltamogram of this complex in CH2C12 shows three reversible one-electron-transfer processes at = 1.19 V, —1.30 V, and — 1.82V (vs. Fc+/Fc), of which the first is a one-electron oxidation, while the other two correspond to two successive one-electron reductions. The spectroscopic data allow one to assign these processes as follows ([174]1 is a one-electron reduced radical form of [174] ) [Nini(174)°2]3+ [NiII(174)02]21 - " [NiI(174)°2]+ = " [NiI(174)°(174)1 ]°. 

Cyclic voltammograms of DTT-TTF, 86a and 86b, exhibited two reversible one-electron transfer processes corresponding to the successive formation for the stable cation radical and dication <2003JMC1324>. 

The mechanism and sequence of events that control delivery of protons and electrons to the FeMo cofactor during substrate reduction is not well understood in its particulars.8 It is believed that conformational change in MoFe-protein is necessary for electron transfer from the P-cluster to the M center (FeMoco) and that ATP hydrolysis and P release occurring on the Fe-protein drive the process. Hypothetically, P-clusters provide a reservoir of reducing equivalents that are transferred to substrate bound at FeMoco. Electrons are transferred one at a time from Fe-protein but the P-cluster and M center have electron buffering capacity, allowing successive two-electron transfers to, and protonations of, bound substrates.8 Neither component protein will reduce any substrate in the absence of its catalytic partner. Also, apoprotein (with any or all metal-sulfur clusters removed) will not reduce dinitrogen. 

Interfacial electron transfer is the critical process occurring in all electrochemical cells in which molecular species are oxidized or reduced. While transfer of an electron between an electrode and a solvated molecule or ion is conceptually a simple reaction, rates of heterogeneous electron transfer processes depend on a multitude of factors and can vary over many orders of magnitude. Since control of interfacial electron transfer rates is usually essential for successful operation of electrochemical devices, understanding the kinetics of these reactions has been and remains a challenging and technologically important goal. 

A first type of reaction that may affect the first electron transfer intermediate is its reduction (or oxidation) at the electrode. In most cases, the second electron transfer is energetically more costly than the first (for a discussion of exceptions to this rule, see Section 1.5). The two processes thus occur at successive values of the electrode potential. There is therefore no difficulty in preventing the occurrence of the second reaction by an appropriate adjustment of the electrode potential. 

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