Homogeneous inner-sphere reactions

Bridge mediation mechanisms in heterogeneous outer sphere electrochemical reactions has also been theoretically treated using the pull—push and push-pull mechanistic concepts [84]. Schmidt [85] has considered theoretically homogeneous inner sphere bridge electron transfer reactions without atom or ion transfer. Bridge mediation in electron transfer reactions may also involve simultaneous atom or ion transfer. Heyrovsky [86] invoked mediation of electron transfer by formation of bridges to explain the enhancement of the rate of electroreduction of indium (III) ions in the presence of specifically adsorbed halide ions on mercury. 

Figure 3.6.1 Outer-sphere and inner-sphere reactions. The inner sphere homogeneous reaction produces, with loss of H2O, a ligand-bridged complex (shown above), which decomposes to CrCl(H20) + and Co(NH3)5(H20). In the heterogeneous reactions, the diagram shows a metal ion (M) surrounded by ligands. In the inner sphere reaction, a ligand that adsorbs on the electrode and bridges to the metal is indicated in a darker color. An example of the latter is the oxidation of Cr(H20)5 at a mercury electrode in the presence of Cl or Br .

A more interesting situation is found when the homogeneous redox reaction is combined with a chemical reaction between the electrocatalyst and the substrate. In this case, the catalytic process is called chemical catalysis. 3 This mechanism is depicted in Scheme 2 for reduction. The coupling of the electron transfer and the chemical reaction takes place via an inner-sphere mechanism and involves the formation of a catalyst-substrate [MC-S] complex. Here the selectivity of the mechanism is determined by the chemical step. Metal complexes are ideal candidates... 

Redox electrode reactions on metal electrodes constitute the simpler case for a theoretical approach to the problem. In particular, outer sphere redox electrode reactions not involving specific adsorption interactions have been treated successfully in analogy with homogeneous redox reactions in solution [54, 56], Approximate extension of the theoretical approach to the case of inner sphere redox reactions at electrodes has been done [56, 57b]. 

Two types of redox catalysts are used in indirect electrolyses [3] (1) pure, outer-sphere, or non-bonded electron transfer agents, and (2) redox reagents that undergo a homogeneous chemical reaction that is intimately combined with a redox step. This may be called inner-sphere electron transfer or bonded electron transfer mechanism. 

Sulfur atoms in thiolate or thioether ligands are well known for their ability to mediate electron transfer in homogeneous redox reactions indeed, in reactions involving chromium(II), a Crm—S bond is often found in the product, indicating an inner sphere mechanism. 

There are several demands that must be more or less fulfilled by the mediator before a successfull amperometric detection of NADH with CMEs can be realized. Despite having a E° lower or comparable with the optimal working potential range for amperometric detection, the mediator should exhibit fast reaction rates both with the electrode proper and NADH, and also be chemically stable at any redox state. Furthermore, the redox reaction of the mediator should involve two electrons and at least one proton making possible, at least theoretically, a fast inner sphere hydride transfer in the homogeneous reaction with NADH. 

In the second chapter, Appleby presents a detailed discussion and review in modem terms of a central aspect of electrochemistry Electron Transfer Reactions With and Without Ion Transfer. Electron transfer is the most fundamental aspect of most processes at electrode interfaces and is also involved intimately with the homogeneous chemistry of redox reactions in solutions. The subject has experienced controversial discussions of the role of solvational interactions in the processes of electron transfer at electrodes and in solution, especially in relation to the role of Inner-sphere versus Outer-sphere activation effects in the act of electron transfer. The author distils out the essential features of electron transfer processes in a tour de force treatment of all aspects of this important field in terms of models of the solvent (continuum and molecular), and of the activation process in the kinetics of electron transfer reactions, especially with respect to the applicability of the Franck-Condon principle to the time-scales of electron transfer and solvational excitation. Sections specially devoted to hydration of the proton and its heterogeneous transfer, coupled with... 

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