Electron Transfer Reactions in Organic Chemistry

Nelsen, Stephen F.

doi:10.1002/9783527618248.ch10

Cited by 21 publications

(26 citation statements)

References 293 publications

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“…35 As expected, the ∆IP value of floppy amines such as TEA and TPA is larger than that of rigid amines such as MANX and DABCO, but there is no correlation between ∆IP and the steric crowding. Thus, λ i seems not to be responsible for the variation of k BET observed here.…”

Section: Discussionmentioning

confidence: 60%

Effect of Steric Hindrance on the Dynamics of Charge Recombination within Geminate Ion Pairs

Vauthey

2000

J. Phys. Chem. A

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The dynamics of charge recombination within geminate ion pairs formed by electron transfer (ET) quenching of excited aromatic hydrocarbons by aliphatic and aromatic amines was investigated using picosecond transient grating spectroscopy. With aliphatic donors, the rate constant of back ET, k BET , shows a substantial decrease with increasing steric encumbrance around the N atom. No correlation between k BET and the exergonicity of the process was observed. This effect is ascribed to a decrease of the electronic coupling matrix element, V, which is affected by both the distance between the N atom of the donor and the aromatic plane of the acceptor and by the delocalization of the hole upon increasing the bulkiness of the alkyl substituents. With aromatic amines, k BET is substantially slower than with the unhindered amines. This is also explained in terms of a smaller value of V because of charge delocalization.

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Section: Discussionmentioning

confidence: 60%

Effect of Steric Hindrance on the Dynamics of Charge Recombination within Geminate Ion Pairs

Vauthey

2000

J. Phys. Chem. A

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“…Strong electron-withdrawing groups have indeed been shown to reinforce fragments clustering. [28][29][30][31][32] To clearly ascertain the nature of the first electron transfer and to unravel the extent of the in-cage interactions between the radical/anion fragments upon electrochemical reduction, compounds 1a-g were further investigated through application of both the ''classical'' dissociative ET model (eqn (3)) and the ''sticky'' dissociative ET model (eqn (5)). This required comparison of the activation free energy of the reactions, as a function of the driving force, obtained through these two models with the experimental one obtained using convolution analysis [77][78][79] of the cyclic voltammetric data.…”

Section: Electrolysesmentioning

confidence: 99%

“…Its fundamental role in areas including organic synthesis and biological processes is well-known. [4][5][6][7][8] To reach a molecular understanding of these processes a rigorous description of the nature and fundamental steps involved in the electron transfer and the subsequent steps is required. Understanding the occurrence of the electron transfer and the factors that control it is therefore necessary.…”

Section: Introductionmentioning

confidence: 99%

Application of the dissociative electron transfer theory and its extension to the case of in-cage interactions in the electrochemical reduction of arenesulfonyl chlorides

Houmam

Hamed

2012

Phys. Chem. Chem. Phys.

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Important aspects of the electrochemical reduction of a series of substituted arene sulfonyl chlorides are investigated. An interesting autocatalytic mechanism is encountered where the starting material is reduced both at the electrode and through homogeneous electron transfer from the resulting sulfinate anion. This is due to the homogenous electron transfer from the two-electron reduction produced anion (arene sulfinate) to the parent arene sulfonyl chloride. As a result, the reduction process and hence the generated final products depend on both the concentration of the substrate and the scan rate. A change is also observed in the reductive cleavage mechanism as a function of the substituent on the phenyl ring of the arene sulfonyl chloride. With 4-cyano and 4-nitrophenyl sulfonyl chlorides a "sticky" dissociative ET mechanism takes place where a concerted ET mechanism leads to the formation of a radical/anion cluster before decomposition. With other substituents (MeO, Me, H, Cl, and F) a "classical" dissociative ET is followed, where the ET and bond cleavage are simultaneous. The dissociative electron transfer theory, as well as its extension to the case of strong in-cage interactions between the produced fragments, along with gas phase chemical quantum calculations results helped us to rationalize both the observed change in the ET mechanism and the occurrence of the "sticky" dissociative ET mechanism. The radical/anion pair interactions have been determined both in solution as well as in the gas phase. The study also shows that despite the low magnitude of in-cage interactions in acetonitrile compared to the gas phase their existence strongly affects the dynamics of the involved reactions. It also shows that, as expected, these interactions are reinforced by the existence of strong electron-withdrawing substituents. The occurrence of an autocatalytic process and the existence of the radical/anion interaction may explain the differences previously observed in the reduction of these compounds in different media.

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“…This research further reveals the importance of hot electrons in chemical reactions by accomplishing reactions that cannot be performed in traditional organic chemistry. 17,18 Such a technique is a promising avenue for exploring continuous plasmon-assisted reactions driven by hot electrons.…”

Section: ■ Introductionmentioning

confidence: 99%

Surface Plasmon-Induced Hot Electrons as the Racemate to Regulate Ionization

Yang

Gao

et al. 2020

J. Phys. Chem. C

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Plasmon-assisted reactions have different reaction mechanisms than conventional chemical reactions occurring in solutions, and the hot electrons produced by plasmon decay play an irreplaceable role in plasmon-assisted coupling reactions. Here, we use p-mercaptobenzoic acid (pMBA) to illustrate this point from different aspects. In a typical chemical reaction, a base is added to deprotonate the carboxylic acid group in pMBA. In this system, however, there is no alkali or external charge to remove the hydrogen, but it is obvious that this system is a dynamic process. Here, although a Lewis base (Ag NPs) was used as the base, the generated hot electrons were trapped by hydrogen ions in an acidic environment, which reduced the efficiency of the ionization reaction. We used SERS to study the ionization of pMBA and to propose a method to regulate its ionization by adjusting its substituents. Furthermore, in contrast to previous studies, the direction of electron flow is clearly defined in this reaction system.

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Electron Transfer Reactions in Organic Chemistry

Cited by 21 publications

References 293 publications

Effect of Steric Hindrance on the Dynamics of Charge Recombination within Geminate Ion Pairs

Effect of Steric Hindrance on the Dynamics of Charge Recombination within Geminate Ion Pairs

Application of the dissociative electron transfer theory and its extension to the case of in-cage interactions in the electrochemical reduction of arenesulfonyl chlorides

Surface Plasmon-Induced Hot Electrons as the Racemate to Regulate Ionization

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