Electroreduction and Reductions with Metals

Dissolving metal reductions were among the first reductions of organic compounds discovered some 130 years ago. Although overshadowed by more universal catalytic hydrogenation and metal hydride reductions, metals are still used for reductions of polar compounds and selective reductions of specific types of bonds and functions. Almost the same results are obtained by electrolytic reduction. 

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In this section primarily reductions of aldehydes, ketones, and esters with sodium, lithium, and potassium in the presence of TCS 14 are discussed closely related reductions with metals such as Zn, Mg, Mn, Sm, Ti, etc., in the presence of TCS 14 are described in Section 13.2. Treatment of ethyl isobutyrate with sodium in the presence of TCS 14 in toluene affords the O-silylated Riihlmann-acyloin-condensation product 1915, which can be readily desilylated to the free acyloin 1916 [119]. Further reactions of methyl or ethyl 1,2- or 1,4-dicarboxylates are discussed elsewhere [120-122]. The same reaction with trimethylsilyl isobutyrate affords the C,0-silylated alcohol 1917, in 72% yield, which is desilylated to 1918 [123] (Scheme 12.34). Likewise, reduction of the diesters 1919 affords the cyclized O-silylated acyloin products 1920 in high yields, which give on saponification the acyloins 1921 [119]. Whereas electroreduction on a Mg-electrode in the presence of MesSiCl 14 converts esters such as ethyl cyclohexane-carboxylate via 1922 and subsequent saponification into acyloins such as 1923 [124], electroreduction of esters such as ethyl cyclohexylcarboxylate using a Mg-electrode without Me3SiCl 14 yields 1,2-ketones such as 1924 [125] (Scheme 12.34). 

Alternatively, CO2 can be used as source of CO. Indeed, it is well known that low-valent transition metal complexes can catalyze the chemical or electrochemical reduction of CO2 into CO. This approach was used to generate the mixed nickel complex Ni°bpy(CO)2 by the electrochemical reduction of Nibpy in NMP or DMF in the presence of CO2. The reduced complex can react with alkyl, benzyl, and allylhalides to give the symmetrical ketone along with the regeneration of Nibpy ". A two-step method alternating electroreduction and chemical coupling leading to the ketone has thus been set up (Scheme 9) [126,127]. 

Electrochemical hydrogenolysis of allylic and benzylic centers can be achieved, but application of this reduction has not been either widely used or acclaimed. It is less convenient experimentally than the comparable method using dissolving metals and control of selectivity is more difficult to achieve than with other methods. Only limited applications are found. Generally electroreduction is carried out using cathodes of metals of high overvoltage such as copper, cadmium, lead and mercury, with anodes of platinum. 

The ACF/Fe and ACF/Ni catalysts, however showed significant activity for CO2 reduction. These results can be imderstood in the light of the work of Kara et al. on electrochemical reduction with high pressure C02[2]. Iron and nickel bulk electrodes show fittle activity for CO2 reduction at ambient pressure. However, with high pressure CO2, these metals showed high activity for CO2 reduction. In this case, we achieved electroreduction imder high pressure-like conditions assisted by the nanospace effect. 

The cationic species also affects the CO2 reduction at metal electrodes. Paik et al. studied electroreduction of CO2 to HCOO at a Hg pool electrode in Li , Na and (C2H5)4N hydrogen-carbonate solutions. The electrode potential at a constant current increases in the positive direction with the sequence of Li < Na < (C2H s)4N . The results were discussed in connection with the vari-... 

Modification of PANI-coated electrodes with metal tetrasul-fonated phthalocyanines (MeTSPc), where the metal is cobalt or iron, resulted in significant changes in the electrocatalysis of the reduction of diojygen [504]. Obviously, insertion of the MeTsPc into the polymer occurs [505]. This was supported in an investigation by Coutanceau et al. by the results of in situ UV-vis spectroscopy. The role of the polymer in the mechanism and the kinetics of dioxygen electroreduction seemed to be somewhat difficult to elucidate. Insertion of CoTsPc resulted in a positive shift of the onset of dioxygen reduction. The two-electron pathway that results in hydrogen peroxide as a reduction product remains. 

The same catalysts and conditions may operate for both reaction directions, that is, either towards the synthesis of methanol or towards its oxidation. Again, CO2 reduction must be able to compete with the electrochemical reduction of water-yielding hydrogen gas. Thermodynamically, the reduction of CO2 to CH3OH is slightly more favourable than the reduction of water. Kinetically, CO2 reduction can be favoured by electrodes, which act as poor catalysts for water reduction, including metallic Mo, Cu, In, Sn and Sb. Using nearly neutral electrolytes, rather than acidic ones, rendered CO2 reduction kinetically more favourable [148]. A detailed mechanism of the mediated electroreduction of carbon dioxide to methanol is addressed in the next section. 

The detailed mechanism dictating the regulation of the process depends on the specific nature of the system, i.e., on the particular compound to be deposited, complexing agent, solution pH, film thickness, potential, etc. For example, in the case of the Cd-Se system, electroreduction of selenosulfate occurs at more positive potentials for either EDTA-ammonia- or NTA-complexed cadmium [13], whereas for ZnSe, the potential required for the reduction of selenosulfate is already reducing for zinc, implying thus a different mechanism. The metal complex has to be adequately stable and should not interfere with selenosulfate reduction. In these terms. 

Hiratsuka et al102 used water-soluble tetrasulfonated Co and Ni phthalocyanines (M-TSP) as homogeneous catalysts for C02 reduction to formic acid at an amalgamated platinum electrode. The current-potential and capacitance-potential curves showed that the reduction potential of C02 was reduced by ca. 0.2 to 0.4 V at 1 mA/cm2 in Clark-Lubs buffer solutions in the presence of catalysts compared to catalyst-free solutions. The authors suggested that a two-step mechanism for C02 reduction in which a C02-M-TSP complex was formed at ca. —0.8 V versus SCE, the first reduction wave of M-TSP, and then the reduction of C02-M-TSP took place at ca. -1.2 V versus SCE, the second reduction wave. Recently, metal phthalocyanines deposited on carbon electrodes have been used127 for electroreduction of C02 in aqueous solutions. The catalytic activity of the catalysts depended on the central metal ions and the relative order Co2+ > Ni2+ Fe2+ = Cu2+ > Cr3+, Sn2+ was obtained. On electrolysis at a potential between -1.2 and -1.4V (versus SCE), formic acid was the product with a current efficiency of ca. 60% in solutions of pH greater than 5, while at lower pH... 

Coin-cyclam322-324 and Nin-cyclam322 catalyze the electroreduction of nitrate in aqueous electrolytes with good current efficiencies and turnover numbers, giving mixtures of ammonia, nitrite, and hydroxylamine at a variety of electrode materials. Mechanistic investigations suggested the adsorption of electroreduced Co1- and Ni1 cyclam onto the electrode surface,322 and the formation of an oxo-metal bond via reduction of coordinated nitrate.323... 

One possible strategy in the development of low-overpotential methods for the electroreduction of C02 is to employ a catalyst in solution in the electrochemical cell, A few systems are known that employ homogeneous catalysts and these are based primarily on transition metal complexes. A particularly efficient catalyst is (Bipy)Re[CO]3Cl, where Bipy is 2,2 bipyridine, which was first reported as such by Hawecker et al. in 1983. In fact, this first report concerned the photochemical reduction of C02 to CO. However, they reasoned correctly that the complex should also be capable of catalysing the electrochemical reduction reaction. In 1984, the same authors reported that (Bipy)Re[C013CI catalysed the reduction of C02 to CO in DMF/water/ tetraalkylammonium chloride or perchlorate with an average current efficiency of >90% at —1.25 V vs. NHE (c. —1.5V vs. SCE). The product analysis was performed by gas chromatography and 13C nmr and showed no other products. 

The method for preparation of polygermanes by reduction of organodichlorogermanes with alkali metals was replaced by electroreduction of organodichlorogermanes and silanes on magnesium cathodes214. The conditions were mild and safe and the product had a satisfactorily defined weight distribution. Ge—Ge and Ge—Si bonds are successfully created. The following test reactions have been performed to show that conditions are indeed favorable for metal-metal bond formation ... 

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