A simple model for the kinetics of dissociative electron transfer in polar solvents. Application to the homogeneous and heterogeneous reduction of alkyl halides
01 Oct 1987-Journal of the American Chemical Society (American Chemical Society)-Vol. 109, Iss: 22, pp 6788-6795
About: This article is published in Journal of the American Chemical Society.The article was published on 1987-10-01. It has received 376 citations till now. The article focuses on the topics: Alkyl & Marcus theory.
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...The OSET activation step of a metal-free ATRP was subsequently carefully evaluated by modified Marcus theory.[145-148] Based on calculations, the ground state Ph-PTZ could not...
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TL;DR: The field of electron transfer processes has been studied extensively in chemistry, electrochemistry, and biology as discussed by the authors, and some history, recent trends, and my own involvement are described.
417 citations
TL;DR: The absolute potential of the standard hydrogen electrode, SHE, was calculated on the basis of a thermodynamic cycle involving H(2(g)) atomization, ionization of H((g))* to H(( g))(+), and hydration of H(+) to obtain a SHE value based on the chemical potential.
Abstract: The absolute potential of the standard hydrogen electrode, SHE, was calculated on the basis of a thermodynamic cycle involving H2(g) atomization, ionization of H(g)• to H(g)+, and hydration of H+. The most up-to-date literature values on the free energies of these reactions have been selected and, when necessary, adjusted to the electron convention Fermi−Dirac statistics since both e− and H+ are fermions. As a reference state for the electron, we have chosen the electron at 0 K, which is the one used in computational chemistry. Unlike almost all previous estimations of SHE, ΔGaq⊖(H+) was used instead of the real potential, αaq(H+). This choice was made to obtain a SHE value based on the chemical potential, which is the appropriate reference to be used in theoretical computations of standard reduction potentials. The result of this new estimation is a value of 4.281 V for the absolute potential of SHE. The problem of conversion of standard reduction potentials (SRPs) measured or estimated in water to the c...
375 citations
TL;DR: In this paper, the dynamics of concerted electron-transfer/bond-breaking reactions can be modeled and the contribution of bond breaking to the activation barrier is discussed, as well as thermal heterogeneous and homogeneous reactions and molecular parameters that govern the concerted/stepwise dichotomy.
Abstract: Publisher Summary Single electron transfer to or from molecules is often accompanied by other reactions involving the formation or the cleavage of bonds. The high energy intermediates thus formed can undergo further electron transfer with the same electron source or sink that initiated the reaction. Among the reactions accompanying electron transfer, bond breaking is a common mode by which a free radical and a diamagnetic leaving group are produced by single electron transfer to a diamagnetic molecule. Such reactions bridge single electron-transfer chemistry and radical chemistry. This chapter explores how the dynamics of concerted electron-transfer/bond-breaking reactions can be modeled and the contribution of bond breaking to the activation barrier. It discusses thermal heterogeneous and homogeneous reactions and molecular parameters that govern the concerted/stepwise dichotomy. The dynamics of the cleavage and coupling reactions and the electron transfer/bond breaking process are examined. Most investigations of dissociative electron transfer concerns thermal reactions and photoinduced-dissociative electron transfer. Quantum yield expressions for the concerted and stepwise cases are established and experimental examples are discussed.
353 citations