Electron transfer acceptor radical anions

Photoinduced single-electron transfer followed by fragmentation of the radical cation is an efficient method for generating carbon-centered radicals under exceptionally mild conditions. The fate of the thus formed radicals depends primarily on their interaction with the acceptor radical anions. Typically observed reactions are either back-electron transfer or radical coupling, but from the synthetic point of view, another most intriguing possibility is the trapping of the radical with suitable substrates such as olefins (Scheme 16). 

In summary, the electron transfer reactions of amines offer an interesting variety of pathways, involving free radical or ionic intermediates and leading to two-electron oxidation as well as coupling and fragmentation reactions. In many systems, however, the most important reaction involves electron return from the acceptor radical anion, i.e. quenching of an excited state without net chemical change. 

The electron transfer from aromatic radical anions to various electron acceptors takes place efficiently in solution. Likewise, when a second solute, pyrene, is added to the MTHF solution of PVB, the electrons transfer from polymer anions to pyrene occurs [50]. The rate constant determined by pulse radiolysis is approximately a third of that of the electron transfer from biphenyl anion to pyrene. 

Type III A non-absorbing molecule transports the electron or the hole after the first electron-transfer step to the target species and thus enable separation of the originally formed acceptor radical anion-donor radical cation pair. This mediator is often used in catalytic amounts but can also be consumed during the PET reaction. In many of these cases, mediators serve as the terminal proton-hydrogen donors. 

Early studies of the distance dependence of ET dynamics focused on intramolecular electron-spin transfer in radical anions containing two equivalent Ti-moieties separated by a hydrocarbon bridge (Figure 8). One of these moieties, which houses the unpaired electron, functions as the donor, while the other (neutral) is an acceptor. ESR studies of the radieal anions of a, ct -diarylalkanes, Ar-(CH2) -Ar 1( ) and re-... 

The termination step of a propagating chain could involve proton transfer to monomer, combination with the acceptor radical anion, or electron transfer from the acceptor radical anion to the carbonium ion to yield a terminal radical, as below. 

As demonstrated in this chapter, there have always been the fundamental mechanistic questions in oxidation of C-H bonds whether the rate-determining step is ET, PCET, one-step HAT, or one-step hydride transfer. When the ET step is thermodynamically feasible, ET occurs first, followed by proton transfer for the overall HAT reactions, and the HAT step is followed by subsequent rapid ET for the overall hydride transfer reactions. In such a case, ET products, that is, radical cations of electron donors and radical anions of electron acceptors, can be detected as the intermediates in the overall HAT and hydride transfer reactions. The ET process can be coupled by proton transfer and also by hydrogen bonding or by binding of metal ions to the radical anions produced by ET to control the ET process. The borderline between a sequential PCET pathway and a one-step HAT pathway has been related to the borderline between the outer-sphere and inner-sphere ET pathways. In HAT reactions, the proton is provided by radical cations of electron donors because the acidity is significantly enhanced by the one-electron oxidation of electron donors. An electron and a proton are transferred by a one-step pathway or a sequential pathway depending on the types of electron donors and acceptors. When proton is provided externally, ET from an electron donor that has no proton to be transferred to an electron acceptor (A) is coupled with protonation of A -, when the one-electron reduction and protonation of A occur simultaneously. The mechanistic discussion described in this chapter will provide useful guide to control oxidation of C-H bonds. 

Donor/Acceptor Systems Upon excitation, a monomer donor (e.g., styrene) undergoes an electron transfer with a monomer acceptor (e.g., maleic anhydride). Then, the donor radical cation and the acceptor radical anion can recombine to form a biradical a recent review was provided in Ref. [193]. 

A bsolute rate constants for electron transfer reactions of some aromatic molecules in solution have been reported in our earlier work (2) using the pulse radiolysis method. The transfer of an electron from various radical anions to a second aromatic compound in solution was observed directly. Of the rate constants for nine donor-acceptor pairs investigated, two were found to be lower than the diffusion controlled values, and a correlation with such parameters as the reduction potential difference of the pair was considered. These measurements have been extended to additional transfer pairs for which the reduction potential difference is small. The objective of this work, in addition to furnishing new data for electron transfer rates, is to provide an adequate test of theories of the rate of homogeneous electron transfer in polar liquids (10, 11,12,13, 14, 15,16,17). 

The transfer of one electron to a single bond leads to a "3-electron bond, a radical anion. Its stability is heavily dependent on the nature and structure of the acceptor, but generally breakage occurs. ... 

Figure C3.2.10.(a) Dependence of electron transfer rate upon reaction free energy for ET between biphenyl radical anions and various organic acceptors. Experiments were perfonned with the donors and acceptors frozen into...

A good example is the excited state of the tris(bipyridine)ruthenium(2+) ion, Ru(bpy)5+. This species results from the transfer of an electron from the metal to a ligand. In the language of localized valences, it is a ruthenium(3+) ion, coordinated to two bipyridines and to one bipyridyl radical anion in other words, [Ru3+(bpy)2(bpy )]2+. This excited state is a powerful electron donor and acceptor.17 The following equations show an example of each quenching mode ... 

The radical anions of dialkyl sulfoxides (or sulfones) may be obtained by direct capture of electron during y-irradiation. It was shown that electron capture by several electron acceptors in the solid state gave anion adducts 27. It was concluded276 that these species are not properly described as radical anions but are genuine radicals which, formed in a solid state cavity, are unable to leave the site of the anions and exhibit a weak charge-transfer interaction which does not modify their conformation or reactivity appreciably, but only their ESR spectra. For hexadeuteriodimethyl sulfoxide in the solid state, electron capture gave this kind of adduct 278,28 (2H isotopic coupling 2.97 G is less than 3.58 G normally found for -CD3). 

The electrophilic character of sulfur dioxide does not only enable addition to reactive nucleophiles, but also to electrons forming sulfur dioxide radical anions which possess the requirements of a captodative" stabilization (equation 83). This electron transfer occurs electrochemically or chemically under Leuckart-Wallach conditions (formic acid/tertiary amine - , by reduction of sulfur dioxide with l-benzyl-1,4-dihydronicotinamide or with Rongalite The radical anion behaves as an efficient nucleophile and affords the generation of sulfones with alkyl halides " and Michael-acceptor olefins (equations 84 and 85). 

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