Co-reductions

Ca.ta.lysis, Iridium compounds do not have industrial appHcations as catalysts. However, these compounds have been studied to model fundamental catalytic steps (174), such as substrate binding of unsaturated molecules and dioxygen oxidative addition of hydrogen, alkyl haHdes, and the carbon—hydrogen bond reductive elimination and important metal-centered transformations such as carbonylation, -elimination, CO reduction, and... 

Stable oxides, such as those of clrromium, vanadium and titanium cannot be reduced to the metal by carbon and tire production of these metals, which have melting points above 2000 K, would lead to a refractoty solid containing carbon. The co-reduction of the oxides widr iron oxide leads to the formation of lower melting products, the feno-alloys, and tlris process is successfully used in industrial production. Since these metals form such stable oxides and carbides, tire process based on carbon reduction in a blast furnace would appear to be unsatisfactory, unless a product samrated with carbon is acceptable. This could not be decarburized by oxygen blowing without significairt re-oxidation of the refractory metal. 

CO Reduction in the ability of the circulatory system to transport O Impairment of performance on tasks requiring vigilance Aggravation of cardiovascular disease. 

The NO reduction over Cu-Ni-Fe alloys has been studied recently by Lamb and Tollefson. They tested copper wires, stainless steel turnings, and metal alloys from 378 to 500°C, at space velocities of 42,000-54,000 hr-1. The kinetics is found to be first order with respect to hydrogen between 400 and 55,000 ppm, and zero order with respect to NO between 600 and 6800 ppm 104). The activation energies of these reactions are found to be 12.0-18.2 kcal/mole. Hydrogen will reduce both oxygen and NO when they are simultaneously present. CO reduction kinetics were also studied over monel metals by Lunt et al. 43) and by Fedor et al. 105). Lunt speculated that the mechanism begins by oxidant attack on the metal surface... 

Metal-induced reductive dimerization of carbonyl compounds is a useful synthetic method for the formation of vicinally functionalized carbon-carbon bonds. For stoichiometric reductive dimerizations, low-valent metals such as aluminum amalgam, titanium, vanadium, zinc, and samarium have been employed. Alternatively, ternary systems consisting of catalytic amounts of a metal salt or metal complex, a chlorosilane, and a stoichiometric co-reductant provide a catalytic method for the formation of pinacols based on reversible redox couples.2 The homocoupling of aldehydes is effected by vanadium or titanium catalysts in the presence of Me3SiCl and Zn or A1 to give the 1,2-diol derivatives high selectivity for the /-isomer is observed in the case of secondary aliphatic or aromatic aldehydes. 

A variety of such ternary catalytic systems has been developed for diastereoselective carbon-carbon bond formations (Table). A Cp-substituted vanadium catalyst is superior to the unsubstituted one,3 whereas a reduced species generated from VOCl3 and a co-reductant is an excellent catalyst for the reductive coupling of aromatic aldehydes.4 A trinuclear complex derived from Cp2TiCl2 and MgBr2 is similarly effective for /-selective pinacol coupling.5 The observed /-selectivity may be explained by minimization of steric effects through anti-orientation of the bulky substituents in the intermediate. 

Borides of Group Va. The borides of Group Va, Nb2, and TaB2, are more difficult to deposit than those of Group IVa, since the incorporation of free metal in the deposit is difficult to avoid. However, relatively pure deposits can be obtained by the co-reduction of the bromides at high temperatures (1500°C) and low pressure, or by the coreduction of the chlorides if the molar gas mixture is preheated to 700-800°C just before entering the reactor.t ] The incorporation of free... 

The CVD of the III-V compounds is usually obtained by reacting an alkyl of a Group-IIIb element with a hydride of a Group-Vb element. These reactions have largely replaced the co-reduction of the halides, The general reaction is as follows ... 

Titanium diboride whiskers by the hydrogen co-reduction of TiCl4 and BBr3 in the presence of a platinum catalyst. 

The electrochemical preparation of metal chalcogenide compounds has been demonstrated by numerous research groups and reviewed in a number of publications [ 1-3]. For the most part, the methods that have been used comprise (a) cathodic co-reduction of the metal ion and a chalcogen oxoanion in aqueous solution onto an inert substrate (b) cathodic deposition from a solvent containing metal ions and the chalcogen in elemental form (the chalcogens are not soluble in water under normal conditions, so these reactions are carried out in non-aqueous solvents) (c) anodic oxidation of the parent metal in a chalconide-containing aqueous electrolyte. 

The co-reduction of copper and selenium is considered as an exception to Kroger s theory. Current-potential curves in the literature show that deposition of copper is rather compulsory to make the deposition of selenium possible. In fact, although the standard potential for Se(IV) reduction is more positive than that of copper (0.741 and 0.340 V vs. SHE, for selenous acid and cupric ion, respectively), it turns out that Se(IV) alone is reduced at more negative potentials than Cu(II). In the presence of copper, the order is reversed. 

Figure 12 Change in CO vibration on Cu-ZSM-5 upon readsorption of water at RT in 10 kPa, after CO reduction at 770 K.

Scheme 4 Cr(VI) anchoring reaction on silicon membered rings of increasing dimensions (and decreasing strain) and the successive CO-reduction. Surface anchoring sites are those reported in Scheme 2...

The synthesis of bimetallic nanoparticles is mainly divided into two methods, i.e., chemical and physical method, or bottom-up and top-down method. The chemical method involves (1) simultaneous or co-reduction, (2) successive or two-stepped reduction of two kinds of metal ions, and (3) self-organization of bimetallic nanoparticle by physically mixing two kinds of already-prepared monometallic nanoparticles with or without after-treatments. Bimetallic nanoparticle alloys are prepared usually by the simultaneous reduction while bimetallic nanoparticles with core/shell structures are prepared usually by the successive reduction. In the preparation of bimetallic nanoparticles, one of the most interesting aspects is a core/shell structure. The surface element plays an important role in the functions of metal nanoparticles like catal5dic and optical properties, but these properties can be tuned by addition of the second element which may be located on the surface or in the center of the particles adjacent to the surface element. So, we would like to use following marks to inscribe the bimetallic nanoparticles composed of metal 1, Mi and metal 2, M2. 

Chen et al. [82] investigated co-reduction of HAuC and AgN03 with hydrazine by UV-Vis spectra. The... 

The XRD and TEM showed that the bimetallic nanoparticles with Ag-core/Rh-shell structure spontaneously form by the physical mixture of Ag and Rh nanoparticles. Luo et al. [168] carried out structure characterization of carbon-supported Au/Pt catalysts with different bimetallic compositions by XRD and direct current plasma-atomic emission spectroscopy. The bimetallic nanoparticles were alloy. Au-core/Pd-shell structure of bimetallic nanoparticles, prepared by co-reduction of Au(III) and Pd(II) precursors in toluene, were well supported by XRD data [119]. Pt/Cu bimetallic nanoparticles can be prepared by the co-reduction of H2PtClg and CuCl2 with hydrazine in w/o microemulsions of water/CTAB/ isooctane/n-butanol [112]. XRD results showed that there is only one peak in the pattern of bimetallic nanoparticles, corresponding to the (111) plane of the PtCu3 bulk alloy. 

Carbon monoxide dehydrogenase active site CO oxidation / CO, reduction... 

Abstract Recent advances in the metal-catalyzed one-electron reduction reactions are described in this chapter. One-electron reduction induced by redox of early transition metals including titanium, vanadium, and lanthanide metals provides a variety of synthetic methods for carbon-carbon bond formation via radical species, as observed in the pinacol coupling, dehalogenation, and related radical-like reactions. The reversible catalytic cycle is achieved by a multi-component catalytic system in combination with a co-reductant and additives, which serve for the recycling, activation, and liberation of the real catalyst and the facilitation of the reaction steps. In the catalytic reductive transformations, the high stereoselectivity is attained by the design of the multi-component catalytic system. This article focuses mostly on the pinacol coupling reaction. 

Keywords C - C bond formation Co-reductant One-electron reduction Radical Reversible redox cycle... 

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. 

It is important to select stoichiometric co-reductants or co-oxidants for the reversible cycle of a catalyst. A metallic co-reductant is ultimately converted to the corresponding metal salt in a higher oxidation state, which may work as a Lewis acid. Taking these interactions into account, the requisite catalytic system can be attained through multi-component interactions. Stereoselectivity should also be controlled, from synthetic points of view. The stereoselective and/or stereospecific transformations depend on the intermediary structure. The potential interaction and structural control permit efficient and selective methods in synthetic radical reactions. This chapter describes the construction of the catalytic system for one-electron reduction reactions represented by the pinacol coupling reaction. 

The ternary system consisting of a metallic catalyst, a chlorosilane, and a stoichiometric co-reductant has been reported by us for the first time to achieve the catalytic pinacol coupling. The homo coupling of aliphatic aldehydes is catalyzed by CpV(CO)4, Cp2VCl2, or Cp2V in the presence of a chlorosilane and Zn in DME to give the 1,3-dioxolanes 1 via the coupling and acetalization (Scheme 3) [18,19]. 

A vanadium catalyst is essential although the combination of Zn and MejSiCl is capable of reductive dimerization of aldehydes [20]. A reversible redox cycle for the in situ generated low-valent vanadium species mediating the electron transfer is achieved in the presence of Zn as the stoichiometric co-reductant (Scheme 4). 

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