Transition metals reduction potentials

Electropositive metals characterized by low standard reduction potentials (alkali metals. Mg, Zn) have been frequently used for the reduction of transition metal halides in the presence of carbon monoxide. The finely divided reducing metal is previously activated by one of the conventional methods. Ethers are frequently used as reaction media. 

Late transition metal or 3d-transition metal irons, such as cobalt, nickel, and copper, are important for catalysis, magnetism, and optics. Reduction of 3d-transition metal ions to zero-valent metals is quite difficult because of their lower redox potentials than those of noble metal ions. A production of bimetallic nanoparticles between 3d-transi-tion metal and noble metal, however, is not so difficult. In 1993, we successfully established a new preparation method of PVP-protected CuPd bimetallic nanoparticles [71-73]. In this method, bimetallic hydroxide colloid forms in the first step by adjusting the pH value with a sodium hydroxide solution before the reduction process, which is designed to overcome the problems caused by the difference in redox potentials. Then, the bimetallic species... 

One-electron reduction or oxidation of organic compounds provides a useful method for the generation of anion radicals or cation radicals, respectively. These methods are used as key processes in radical reactions. Redox properties of transition metals can be utilized for the efficient one-electron reduction or oxidation (Scheme 1). In particular, the redox function of early transition metals including titanium, vanadium, and manganese has been of synthetic potential from this point of view [1-8]. The synthetic limitation exists in the use of a stoichiometric or excess amount of metallic reductants or oxidants to complete the reaction. Generally, the construction of a catalytic redox cycle for one-electron reduction is difficult to achieve. A catalytic system should be constructed to avoid the use of such amounts of expensive and/or toxic metallic reagents. 

The redox interaction with a co-reductant permits the formation of a reversible redox cycle for one-electron reduction as shown in Scheme 2. Furthermore, the function of transition metals is potentially and sterically controlled by ligands. A more efficient interaction between the orbitals of metals and substrates leads to facile electron transfer. Another interaction with an additive as a Lewis acid towards a substrate also contributes to such electron transfer. 

Potentially coordinatively unsaturated dithiolene-metal complexes are rare,298-306 and 1 1 dithiolene-transition-metal complexes with no other ligands are, to our knowledge, unprecedented.307 The neutral complex [PdS2C2(COOMe)2]6,308 is homoleptic containing one dithiolene unit for each palladium atom and no other ligands. Electrochemical reduction of the compound depicted in Figue 21 proceeds in four reversible steps. 

Equilibrium considerations other than those of binding are those of oxidation/reduction potentials to which we drew attention in Section 1.14 considering the elements in the sea. Inside cells certain oxidation/reductions also equilibrate rapidly, especially those of transition metal ions with thiols and -S-S- bonds, while most non-metal oxidation/reduction changes between C/H/N/O compounds are slow and kinetically controlled (see Chapter 2). In the case of fast redox reactions oxidation/reduction potentials are fixed constants. 

In a different approach a super-high-throughput ee-assay was developed on the basis of chirally modified capillary array electrophoresis (CAE).90 CAE was used in the Human Genome Project, and commercially available instruments have been developed which comprise a high number of capillaries in parallel, for example the 96-capillary unit MegaBACE consisting of 6 bundles of 16 capillaries.91 The system can address a 96-well microtiter plate. It was adapted to perform ee-determinations of chiral amines, which are potentially accessible by catalytic reductive amination of ketones, transition metal catalyzed Markovnikov addition of ammonia, or enzymatic hydrolysis of acetamides (Scheme 14).90... 

In contrast to a variety of oxidizable compounds, only a few examples for the detection of strong oxidants with transition metal hexacyanoferrates were shown. Among them, hydrogen peroxide is discussed in the following section. Except for H202, the reduction of carbon dioxide [91] and persulfate [92] by Prussian blue-modified electrode was shown. The detection of the latter is important in cosmetics. It should be noted that the reduction of Prussian blue to Prussian white occurs at the lowest redox potential as can be found in transition metal hexacyanoferrates. 

These are the less active metals with positive reduction potentials. They are transition metals and can be found in Group 8B and 1B. 

---