Direct and indirect electrochemistry of perfluoroalkyl bromides and iodides. Outersphere electron transfer from 12040t which is. Outersphere dissociative electron transfer to organic molecules. Quantum scaling of strongly interacting systems xueyu song and alexei a. V outersphere electron transfer reactions involving. They are of great importance in nature, but also in technology, and have been in the center of interest during the last 50 years, which is evident from several thousands of publications in the field. Influence of inner and outersphere electron transfer. Such systems offer the possibility to investigate the effects of the local reactant concentrations in the micellar subphase, as well as of. Pdf understanding the difference between inner and outer. Difference between inner and outer sphere mechanism compare. For example, compare the rate constants for the following two electron transfer reactions, involving almost exactly the same complexes. The marcus theory of electron transfer was then extended to include innersphere electron transfer by noel hush and marcus.
For the love of physics walter lewin may 16, 2011 duration. Of course, there are limitations to the distance involved, and the further away the metals, the less likely the reaction. The effect of solvent relaxation dynamics on outersphere. Oxidationreduction reactions of transition metal complexes there are two main mechanisms. Marcus theory for electron transfer chemistry libretexts. Now, we neglect the imaginary part of \gt\ and take the limit. In any transition metal redox process, the mechanism can be assumed to be outer sphere unless the conditions of the inner sphere are met. Outer sphere refers to an electron transfer et event that occurs between chemical species that remain separate and intact before, during, and after the et. Inner sphere reactions generally have one labile and one inert reactant. V for outersphere electron transfer between metal complexes in solution is assessed. Lecture redox reactions between metal ions,the chelate effect, hard and soft acids and bases 1. The term outer sphere electron transfer refers to the transfer of an electron between two species or if intramolecular between two functionalities without the incursion of significant covalent bond formation between the two species or the two functional groups.
Outersphere electron transfer kinetics of metal ion. Rudy marcus at caltech has developed a mathematical approach to understanding the kinetics of electron transfer, in work he did beginning in the late 1950s. Reflections on the outersphere mechanism of electron transfer. It was proposed that an outer sphere electron transfer is promoted by alkaline media on metals 166,167 and fenc 166,168 catalysts. Outer sphere electron transfer mechanism and inner sphere electron transfer mechanism join the revolution by becoming a part of our community and get all of the member benefits like downloading any pdf document absolutely free for. The main theory that describes the rates of outer sphere electron transfer was developed by rudolph a. Electrontransfer reactions are reactions of the oxidativereductive type. Glossary of terms used in physical organic chemistry iupac recommendations 1994 on page 1125 terms paper pac, 1996, 68, 2223.
It, however, is highly challenging to unambiguously prove their outer. Jan 27, 2019 the utilization of photoinduced electron transfer pet reactions is an effective strategy to design various stimuli. The effect of solvent relaxation dynamics on outer sphere electron transfer. The direct evidence of the inner sphere electron transfer in homogeneous reactions is the bridge ligand transfer from the initial inert oxidized form to the final inert. Chem 3030 supplemental materials on electron transfer fundamentals of marcuss adiabatic outer sphere electron transfer theory ehrenfests adiabatic principle states that a system will remain in a definite quantum level if its surroundings are changed sufficiently slowly. Marcus theory is a theory originally developed by rudolph a. The effect of solvent relaxation dynamics on outersphere electron transfer. Aug, 2018 for the love of physics walter lewin may 16, 2011 duration. We will start with a discussion of outersphere degenerate electron transfers those involving transfer between oxidized and reduced forms of the same couple. The electron transfer reaction shown by equation 12 is extremely slow with a rate constant of i 03 m1s1 and can easily be explained in term of outer sphere mechanism. In inner sphere reactions, the electron transfer occurs in an activated complex. To date, most of these materials are based on the inner sphere electron transfer mechanism, which refers to a redox chemical reaction that proceeds via a covalent bridge. Stuchebrukhov arthur amos noyes laboratory of chemical physics, a 12772, california institute of technology, pasa dena, california 91125 received 21 january 1993. Electron transfer reactions, sphere electron transfer reactions, inner sphere electron transfer outer reactions.
Difference between inner and outer sphere mechanism. First one must understand the meaning of oxidation and reduction before going to define the concept. In outersphere redox processes, the interaction between an oxidizing and a reducing agent at the moment of electron transfer is very small. V outersphere electron transfer reactions involving surfactantcobaltiii complexes and fecn6 4ion 5. Outer sphere reductive single electron transfer osset has been proposed for such different processes as vitamin b 12dependent biodegradation and zerovalent metalmediated dehalogenation. In this study, we have chosen to treat only the outer sphere mechanism for eqn. Fundamentals of marcuss adiabatic outer sphere electron. Aug 11, 2019 the key difference between inner and outer sphere mechanism is that the inner sphere electron transfer occurs between complexes via bridging ligands, whereas the outer sphere electron transfer mechanism occurs between complexes that do not undergo substitution. M electronic matrix element of the interaction between the reactant and the electrode k a exp. Marcus, starting in 1956, to explain the rates of electron transfer reactions the rate at which an electron can move or jump from one chemical species called the electron donor to another called the electron acceptor.
It was originally formulated to address outer sphere electron transfer reactions. To get a feeling for the dependence of \k\ on \q\, we can look at the classical limit \\hbar \omega \ll k t\. Marcus developed a theory for treating the rates of outersphere electrontransfer reactions. Other articles where outersphere reaction is discussed. Marcus theory of electron transfer from a molecular perspective, marcus theory is typically applied to outer sphere et between an electron donor d and an electron acceptor a. The key difference between inner and outer sphere mechanism is that the inner sphere electron transfer occurs between complexes via bridging ligands, whereas the outer sphere electron transfer mechanism occurs between complexes that do not undergo substitution. Iv outersphere electron transfer reactions involving. In some cases, electron transfers occur much more quickly in the presence of certain ligands. Outer sphere refers to an electron transfer et event that occurs between chemical species that remain separate and intact before, during, and after the et event. Talk about inner sphere mechanism and how to differentiate bw inner and outer sphere mechanism.
Investigations of the rates of outersphere electron transfer. Pdf outersphere dissociative electron transfer to organic. Pdf outersphere electrontransfer and the effect of linkage. For convenience in this discussion we will assume d and a are neutral molecules so that electrostatic forces may be ignored.
The word redox reaction envisages transfer of electrons, hydrogen atom. A qualitative picture of marcus theory so, what holds the electron back. Electron transfer an overview sciencedirect topics. The utilization of photoinduced electron transfer pet reactions is an effective strategy to design various stimuli. Resolving orbital pathways for intermolecular electron transfer. In contrast, for inner sphere electron transfer the participating redox sites undergoing et become connected by a chemical bridge. The word redox reaction envisages transfer of electron s, hydrogen atom. Redox chemistry iv electron transfer processes outer sphere. When small ions are involved, electron transfer is generally inefficient unless there exists a nearresonance between an energy level of the product ion and an available recombination energy of the reactant ion. Discussion about electron transfer in transition metal complexes. His original article 1956 referred to the self exchange. Kinetics of some outersphere electrontransfer reactions. Preparation, characterization, and outersphere electron. Mccusker in condensed phase chemistry, the solvent can have a signi.
A surface independent outersphere electron transfer component is proposed to be the reason for the socalled facile kinetics of orr in alkaline media on a wide range of nonnoble metal surfaces. Marcus to address outersphere electron transfer and was based on a transitionstate theory approach. Extending this concept of an orbital pathway to nonbonded, formally outersphere electron transfer reactions has proven more challenging. Introduction there are many reports available on the reaction between fecn6 4and metal complexes 14. Compoundspecific isotope effect c 12 c, 37 cl 35 cl analysis offers a. Outersphere electron transfer occurs without dissociation or disruption of the coordination sphere of either complexi. Outersphere reductive single electron transfer osset has been proposed for such different processes as vitamin b 12dependent biodegradation and zerovalent metalmediated dehalogenation. But an outer sphere electron transfer seems a little magical. Because the et in outer sphere electron transfer occurs between two nonconnected species, the. The marcus theory of electron transfer was then extended to include inner sphere electron transfer by noel hush and marcus. Aug 05, 2011 a surface independent outersphere electron transfer component is proposed to be the reason for the socalled facile kinetics of orr in alkaline media on a wide range of nonnoble metal surfaces. Introduction reactions in micellar solutions are often used as models for compartmentalized systems.
Sep 11, 2017 talk about inner sphere mechanism and how to differentiate bw inner and outer sphere mechanism. If the rate of electron transfer is faster than the rate of ligand exchange for both of the reactants must be outer sphere. Marcus to address outer sphere electron transfer and was based on a transitionstate theory approach. Electron transfer reactions are reactions of the oxidativereductive type. Reductive outersphere single electron transfer is an. This long distance hop is called an outer sphere electron transfer. The quantitative efficacy of the stranksmarcushush theory of volumes of activation. The alternative to inner sphere electron transfer is outer sphere electron transfer. Outer sphere dissociative electron transfer to organic molecules. Outersphere reactions are reactions in which an electron is transferred from a donor to an acceptor without any chemical bonds being made or broken.
Quantum theory of electron transfer nonadiabatic reactions the total rate constant when only classical outer sphere modes are reorganized. This corresponds to the case where one is describing the case of a low frequency solvent mode or outer sphere effect on the electron transfer. Stuchebrukhov arthur amos noyes laboratory of chemical physics, a 12772, california institute of technology, pasa dena, california 91125 received 21. Redox chemistry iv electron transfer processes outer. Photochemistry of transition metal complexes induced by. Outer sphere electron transfer occurs between complexes that do not undergo substitution. In outersphere reactions, the electron transfer occurs between two species with no bonding between them, with the electron tunneling from one to the other, probably across a solvation layer. However, this outersphere process predominantly leads only to a 2e peroxide intermediate as the final product. A major aspect of marcus theory is the dependence of the electron transfer rate on the thermodynamic driving force difference in the redox potentials of the electron exchanging sites. In outer sphere reactions, the electron transfer occurs between two species with no bonding between them, with the electron tunneling from one to the other, probably across a solvation layer. Other articles where innersphere reaction is discussed.
Perhaps the most obvious factor that might influence how easily an electron can travel from one metal to another is the nature of the medium through which it must travel. If the rate of electron transfer is much faster than marcus theory would predict based on measuring k 12, k 1 and k 2, there is. Outersphere electrontransfer and the effect of linkage isomerism in the titanium iii reduction of nitropentacyanocobaltateiii and nitro, and. Marcus developed an original theory to explain the rate of et reactions, linking the thermodynamics of the process to its kinetics. The two metals react without ever contacting each other, without getting into each others coordination spheres. Reflections on the outersphere mechanism of electron. Herein, we employ quantitative cyclic voltammetry to assess whether ferrocene carboxylates and sulfonates mediate only outer. Lecture redox reactions between metal ions,the chelate. Inner sphere electron transfer is generally enthalpically more favorable than outer sphere electron transfer due to a. The first generally accepted theory of et was developed by rudolph a.
It was originally formulated to address outer sphere electron transfer reactions, in which the two chemical. Compoundspecific isotope effect c 12 c, 37 cl 35 cl analysis offers a new opportunity to test these hypotheses. V outer sphere electron transfer reactions involving surfactantcobaltiii complexes and fecn6 4ion 5. Intermolecular and outer sphere os electron transfer are frequently used as synonymous expressions. Inorganic mechanisms ii core module 7 richard douthwaite.
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