Electron transfer metal ions

Metals of changing valency influence oxidation rates by complex formation. The ligands are either substrate or enzyme protein molecules or both. Electron distribution is altered as well in the center as in the ligands, providing us with a number of catalysts of graded reactivity. As a consequence of one electron transfer, metal ions of changing valency may initiate chain reactions, whereby the rate of the oxidative process is greatly increased. 

Most of the free-radical mechanisms discussed thus far have involved some combination of homolytic bond dissociation, atom abstraction, and addition steps. In this section, we will discuss reactions that include discrete electron-transfer steps. Addition to or removal of one electron fi om a diamagnetic organic molecule generates a radical. Organic reactions that involve electron-transfer steps are often mediated by transition-metal ions. Many transition-metal ions have two or more relatively stable oxidation states differing by one electron. Transition-metal ions therefore firequently participate in electron-transfer processes. 

Electrodes may be classified into the following two categories as shown in Fig. 4-3 one is the electronic electrode at which the transfer of electrons takes place, and the other is the ionic electrode at which the transfer of ions takes place. The electronic electrode corresponds, for instance, to the case in which the transfer of redox electrons in reduction-oxidation reactions, such as Fe = Fe + e,occurs and the ionic electrode corresponds to the case in which the transfer of ions, such as Fe , , = Fe, occiirs across the electrode interface. Usually, the former is found with insoluble electrodes such as platinum electrodes in aqueous solution containing redox particles and the latter is found with soluble metal electrodes such as iron and nickel. In practice, both electron transfer and ion transfer can take place simultaneously across the electrode interface. 

Fig. 1. Interaction of d-orbital electrons of metal ions with ligands, (a) In a hard acid-hard base combination there is no electron transfer, and the two ions bind by ionic forces, (b) In a soft acid-soft base combination there may be ir-bonding as a result of donation of electrons from the d-orbital of the metal to the ligand the transfer of electrons from metal to ligand prevents the soft metal (usually in a low oxidation state) from becoming too negative.

MV clusters usually exhibit characteristic absorption bands within the infrared or visible spectral ranges. These bands are related to light-induced transfer of the extra electron between metal ions. This absorption is called intervalence. 

There are two types of interfacial potential differences equilibrium and non-equilibrium potentials. (From now on we will use potential as shorthand for potential difference . Potentials of individual phases cannot be measured, but some potential differences can be.) The equilibrium potentials can again be subdivided into two categories electron transfer and ion transfer potentials. The metal/metal ion potentials can be considered as... 

In the case of metallic corrosion, the local cell model assumes that corrosion occurs as a combination of anodic metal oxidation and cathodic oxidant reduction. The anodic metal oxidation (dissolution) is a process of metal ion transfer across the metal-solution interface, in which the metal ions transfer from the metallic bonding state into the hydrated state in solution. We note that, before they transfer into the solution, the metal ions are ionized forming surface metal ions free from the metallic bonding electrons. The metal ion transfer is written as follows ... 

The corrosion potential, defined by the rate of the electrochemical reactions, is a relevant property of corrosion reactions at the metal/adhesive interface as it reflects the kinetics of the electron-transfer and ion-transfer reactions. Depending on the system being observed, correlations exist between the measurable Volta potential difference and the corrosion potential. 

A second class of electrochemical processes in addition to electron transfer is ion transfer, e.g., metal ion transfer according to the equation... 

A variety of reactions are thought to occur via such a mechanism. Some examples with their corresponding (second-order) rate constants are shown in Table 5.5. The entries at the top of the table are self-exchange reactions in which two coordinated ions, identical in everyway except for the oxidation state of the metal, simply exchange an electron. One metal ion is oxidized, the other reduced, but no net reaction actually takes place because the products are indistinguishable from the reactants. The lower set of reactions, called cross reactions, involve a transfer (or a crossing over ) of an electron between different coordinated metal ions. These examples, as shown, do result in net reactions. 

Electrode processes are a class of heterogeneous chemical reaction that involves the transfer of charge across the interface between a solid and an adjacent solution phase, either in equilibrium or under partial or total kinetic control. A simple type of electrode reaction involves electron transfer between an inert metal electrode and an ion or molecule in solution. Oxidation of an electroactive species corresponds to the transfer of electrons from the solution phase to the electrode (anodic), whereas electron transfer in the opposite direction results in the reduction of the species (cathodic). Electron transfer is only possible when the electroactive material is within molecular distances of the electrode surface thus for a simple electrode reaction involving solution species of the fonn... 

Reactions involving the peroxodisulfate ion are usually slow at ca 20°C. The peroxodisulfate ion decomposes into free radicals, which are initiators for numerous chain reactions. These radicals act either thermally or by electron transfer with transition-metal ions or reducing agents (79). 

Hydroperoxides are decomposed readily by multivalent metal ions, ie, Cu, Co, Fe, V, Mn, Sn, Pb, etc, by an oxidation-reduction or electron-transfer process. Depending on the metal and its valence state, metallic cations either donate or accept electrons when reacting with hydroperoxides (45). Either one... 

With most transition metals, eg, Cu, Co, and Mn, both valence states react with hydroperoxides via one electron transfer (eqs. 11 andl2). Thus, a small amount of transition-metal ion can decompose a large amount of hydroperoxide and, consequendy, inadvertent contamination of hydroperoxides with traces of transition-metal impurities should be avoided. 

As with other hydroperoxides, hydroxyaLkyl hydroperoxides are decomposed by transition-metal ions in an electron-transfer process. This is tme even for those hydroxyaLkyl hydroperoxides that only exist in equiUbrium. For example, those hydroperoxides from cycHc ketones (R, R = alkylene) form an oxygen-centered radical initially which then undergoes ring-opening -scission forming an intermediate carboxyalkyl radical (124) ... 

Metal-Catalyzed Oxidation. Trace quantities of transition metal ions catalyze the decomposition of hydroperoxides to radical species and greatiy accelerate the rate of oxidation. Most effective are those metal ions that undergo one-electron transfer reactions, eg, copper, iron, cobalt, and manganese ions (9). The metal catalyst is an active hydroperoxide decomposer in both its higher and its lower oxidation states. In the overall reaction, two molecules of hydroperoxide decompose to peroxy and alkoxy radicals (eq. 5). 

Many reactions catalyzed by the addition of simple metal ions involve chelation of the metal. The familiar autocatalysis of the oxidation of oxalate by permanganate results from the chelation of the oxalate and Mn (III) from the permanganate. Oxidation of ascorbic acid [50-81-7] C HgO, is catalyzed by copper (12). The stabilization of preparations containing ascorbic acid by the addition of a chelant appears to be negative catalysis of the oxidation but results from the sequestration of the copper. Many such inhibitions are the result of sequestration. Catalysis by chelation of metal ions with a reactant is usually accomphshed by polarization of the molecule, faciUtation of electron transfer by the metal, or orientation of reactants. 

Chelation itself is sometimes useful in directing the course of synthesis. This is called the template effect (37). The presence of a suitable metal ion facihtates the preparation of the crown ethers, porphyrins, and similar heteroatom macrocycHc compounds. Coordination of the heteroatoms about the metal orients the end groups of the reactants for ring closure. The product is the chelate from which the metal may be removed by a suitable method. In other catalytic effects, reactive centers may be brought into close proximity, charge or bond strain effects may be created, or electron transfers may be made possible. 

The simplest electroplating baths consist of a solution of a soluble metal salt. Electrons ate suppHed to the conductive metal surface, where electron transfer to and reduction of the dissolved metal ions occur. Such simple electroplating baths ate rarely satisfactory, and additives ate requited to control conductivity, pH, crystal stmcture, throwing power, and other conditions. 

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