The marcus theory of electron transfer was then extended to include inner sphere electron transfer by noel hush and marcus. Outer sphere electron transfer occurs without dissociation or disruption of the coordination sphere of either complexi. Modulation of outersphere electron transfer reactivity. Electronproton transfer theory and electrocatalysis part i.
Mayer1 1department of chemistry, yale university, new haven, ct 065208107, usa. Lecture redox reactions between metal ions,the chelate effect, hard and soft acids and bases 1. Inner sphere electron transfer is mediated by a bridging ligand. Pdf the concepts of inner and outersphere mechanisms for complex charge. In sum, studies of blue copper proteins have elucidated many of the features that tune reduction potentials and promote redox reactions. Sep 10, 2017 discussion about electron transfer in transition metal complexes. The solvent assumes a suitable intermediate nonequilibrium configuration the transition state 3. Some aspects of electrontransfer reaction of ascorbate with. It is of interest that lu and coworkers rationally designed azurins with reduction potentials that span a 700 mv range using only a handful of inner and outer sphere mutations. Discrimination of inner and outer sphere electrode reactions by cyclic voltammetry experiments key words marcus theory, electron transfer, chronoamperometry, chronocoulometry, cyclic voltammetry, electrical double layer object it aims to learn basic concepts of microscopic pictures in electrochemistry and principles of. Unlike in the inner sphere mechanism, there is no bridging between reactants in 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.
Comparison of observed and calculated rate constants for outer sphere electron transfer reactions the values of kl2. Marcus developed a theory for treating the rates of outer sphere electron transfer reactions. Electron transfer reactivity of the aqueous ironiv oxo. Sep 11, 2017 inner sphere electron transfer mechanism gate chemistry.
Outersphere electrontransfer and the effect of linkage isomerism in the titaniumiii reduction of nitropentacyanocobaltateiii and nitro, and. Understanding the difference between inner and outer sphere mechanisms. In contrast, for inner sphere electron transfer the participating redox sites undergoing et become connected by a chemical bridge. 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. Lecture redox reactions between metal ions,the chelate. Outersphere electrontransfer and the effect of linkage isomerism in the titanium iii reduction of nitropentacyanocobaltateiii and nitro, and.
Chemical physics 49 1980 295 304 northholland publishing company outer sphere electron transfer in polar solvents ed. Fundamentals of marcuss adiabatic outer sphere electron. Of course, there are limitations to the distance involved, and the further away the metals, the less likely the reaction. Pegis,1e, zixuan wang, 1,3 gourab banerjee,1 coleen t. Rates of outer sphere electron transfer et reactions, par ticularly selfexchanges, are typically only marginally influenced by environmental factors e. Inner sphere electron transfer chemistry libretexts. In inner sphere reactions, the electron transfer occurs in an activated complex. Understanding the difference between inner and outersphere mechanisms. Talk about inner sphere mechanism and how to differentiate bw inner and outer sphere mechanism. Shape selectivity in outersphere electron transfer reactions article in inorganica chimica acta 3311. 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. Pdf understanding the difference between inner and outer. Pdf outersphere electrontransfer and the effect of linkage. The latter is discussed in the context of a continuous series of outer and innersphere mechanisms for organic electrontransfer processes in a manner originally formulated by taube and coworkers for inorganic coordination donoracceptor dyads with conciliatory attention paid to traditional organic versus inorganic concepts.
Investigations of the rates of outersphere electron transfer. V outersphere electron transfer reactions involving. Pdf synthesis, cmc determination, and outer sphere electron. It was determined that bimolecular rate constants correlate with the singleelectron reduction poten tial. A singleelectron oxidation of ascorbate by a series of lowpotential quinones was investigated. The two metals react without ever contacting each other, without getting into each others coordination spheres.
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. Electron transfer reactions are reactions of the oxidativereductive type. 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. Photochemistry of transition metal complexes induced by outer. The reactions involve quinones, hydrazines, thiols, and 1,3. Calculated electron transfer parameters for the outer sphere metal ion selfexchange reactions are given in table 1. Outer sphere vs protoncoupled electron transfer hajem bataineh, oleg pestovsky, and andreja bakac ames laboratory and chemistry department, iowa state university, ames, iowa 50011, united states s supporting information. V outer sphere electron transfer reactions involving surfactantcobaltiii complexes and fecn6 4ion 5. Advanced inorganic chemistryelectron transfer reactions. The alternative to inner sphere electron transfer is outer sphere electron transfer. Nov 21, 2018 extending this concept of an orbital pathway to nonbonded, formally outer sphere electron transfer reactions has proven more challenging, though considerable progress has been made in the field. But an outer sphere electron transfer seems a little magical.
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. Figure 4 schematic diagrams showing the difference between outer and inner sphere electron transfer reactions and corresponding excess chemical potential energy curves. Marcus to address outer sphere electron transfer and was based on a transitionstate theory approach. An electrochemical experiment article pdf available in journal of chemical education 738.
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. Intermolecular and outer sphere os electron transfer are frequently used as synonymous expressions. Electron transfer reactions in which bonds are made or broken are referred to as inner sphere. They play a special role in that every electrochemical reaction involves at least one electron transfer step. Inner and outersphere metal coordination in blue copper.
In contrast, innersphere reactions occur in an activated complex where the ions share a ligand electron transfer within a primary bond system. This long distance hop is called an outer sphere electron transfer. Iupac outersphere electron transfer o04351 iupac gold book. Outersphere electron transfer kinetics of metal ion. Resolving orbital pathways for intermolecular electron transfer. 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. Electron transfer occurs through the bridge once it is established.
Here we describe the rates of electron transfer between weakly coupled donor and acceptor states when the potential energy depends on a nuclear coordinate, i. Of course, there are limitations to the distance involved, and the. Oxidationreduction reactions of transition metal complexes there are two main mechanisms. In any transition metal redox process, the mechanism can be assumed to be outer sphere unless the conditions of the inner sphere are met. Outersphere electron transfer in polar solvents sciencedirect. In outersphere redox processes, the interaction between an oxidizing and a reducing agent at the moment of electron transfer is very small. Some quantum chemical aspects on outersphere electrontransfer reactions. Kinetics of some outersphere electrontransfer reactions. Introduction reactions in micellar solutions are often. The references in the last column should be consulted for the experimental data. View the article pdf and any associated supplements and figures for a period of 48 hours.
Supporting information unified mechanism of oxygen atom. Mar 28, 2002 read shape selectivity in outer sphere electron transfer reactions, inorganica chimica acta on deepdyve, the largest online rental service for scholarly research with thousands of academic publications available at your fingertips. For example, a reaction that occurs when steel wool. Zusman institute of inorganic chemistry, siberian branch of the soeiet academy of sciences. The quantitative efficacy of the stranksmarcushush theory of volumes of activation a v for outersphere electron transfer between metal complexes. Reactions and applications of coordination compounds. We report here an example where selfexchange rates are. Long range electron transfers such as in cytochromes are most likely to occur by outer sphere mechanisms. Electron transfer reactions in which bonds are made or broken are referred to as inner sphere reactions. Electron transfer kinetics on nonprecious group metal. The outer sphere mechanism is important because of the analogy that can be drawn between electron transfer in metal complexes and electron transfer in. Unified mechanism of oxygen atom transfer and hydrogen atom transfer reactions with a triflic acidbound nonheme manganeseivoxo complex via outersphere electron transfer yongmin lee, surin kim, kei ohkubo,kyungha kim, wonwoo nam, and shunichi fukuzumi. Electron transfer reactivity of the aqueous ironiv.
Inner sphere and outer sphere electron transfer does not only occur between metals but can also occur between organic compounds. The results were interpreted in the framework of the outersphere electrontransfer theory given by marcus. Discussion about electron transfer in transition metal complexes. 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. Redox chemistry iv electron transfer processes outer. 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. Iv outersphere electron transfer reactions involving. Shape selectivity in outersphere electron transfer. Outer sphere electron transfer reactions in reactions of this type the metal ion retains its full coordination shell and there is a direct electron transfer from the reductant to the oxidant.
The electron transfer between hydroquinone and the fe oxides was monitored by uvvisible and electron spin reso nance spectroscopy. In electron transfer, an electron moves from one atom to another, changing the charge on each but leaving the net charge of the system the same. It is valuable to first discuss the selfexchange reactions for the separate couples, because the molecular properties controlling these reactions also influence the rate of the crossreactions between the metal ions and oxygen. Synthesis, cmc determination, and outer sphere electron transfer reaction of the article pdf available in australian journal of chemistry 668. Inner sphere electron transfer is et or bonded electron transfer is a redox chemical reaction that proceeds via a covalent linkagea strong electronic interactionbetween the oxidant and. Enabled via outer sphere electron transfer onyu jung,1e michael l. Shape selectivity in outersphere electron transfer reactions. For a clean, sustainable, and secure energy future, rechargeable liair batteries attract a great deal of interest for the next generation energy storage and conversion devices because of their extremely high theoretical energy density up to 23 kwhkg.
In the present paper outer sphere electron transfer et reactions in polar media in the limit of fast dielectric relaxation are discussed. Influence of inner and outersphere electron transfer. Introduction reactions in micellar solutions are often used as models for compartmentalized systems. Marcushush theory applies to inner sphere mechanisms. Electron transfer reaction electron transfer reaction is a reaction in which a single electron is transferred from one molecule to another. We will start with a discussion of outer sphere degenerate electron transfers those involving transfer between oxidized and reduced forms of the same couple. The reactant moves close to the electrode surface, but does not adsorb outer helmholtz plane, say 2. Importantly, we find that the heterogeneous electron transfer kinetics of the carbon. A qualitative picture of marcus theory so, what holds the electron back. Inner sphere electron transfer is generally enthalpically more favorable than outer sphere electron transfer due to a larger degree of interaction between the metal centers involved, however, inner sphere electron transfer is usually entropically less favorable since the two sites involved must become more ordered come together via a bridge. Pdf the effect of solvent relaxation dynamics on outer.
These results reflect the findings of marcus theory of electron transfer. In this limit the reaction rate is independent of the relaxation properties of the solvent and can be studied within the traditional statistical equilibrium. Difference between inner and outer sphere mechanism. Outer sphere mechanism of electron transfer is a chemical reaction in which reactants and products exist separate from each other before, during and after the event of electron transfer. In an inner sphere mechanism, electron transfer between two metal centres involves a bridging. 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 a good chance that the reaction is inner sphere. Such systems offer the possibility to investigate the effects of the local reactant concentrations in the micellar subphase, as well as of. Inorganic mechanisms ii core module 7 richard douthwaite. The effect of solvent relaxation dynamics on outer sphere electron transfer. However, this outersphere process predominantly leads only to a 2e peroxide intermediate as the final product. An electrochemical experiment article pdf available in journal of chemical education 738 august 1996 with 3,249 reads. Reflections on the outersphere mechanism of electron transfer. Electron transfer may occur by an inner or outer sphere mechanism depending on the system.
Influence of inner and outersphere electron transfer mechanisms during electrocatalysis of oxygen reduction in alkaline media nagappan ramaswamy and sanjeev mukerjee department of chemistry and chemical biology, northeastern university center for renewable energy technology. The first generally accepted theory of et was developed by rudolph a. Outer sphere reactions are reactions in which an electron is transferred from a donor to an acceptor without any chemical bonds being made or broken. Introduction there are many reports available on the reaction between fecn6 4. There are two different mechanisms of electron transfer redox reactions. Lecture 23 part b electron transfer mechanisms duration. For outer sphere electron transfer, since there is no significant rearrangement of bonds, the.
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