Stepwise reduction

LiAlH4, AIH3 has been used for reduction[9]. Stepwise reduction, first to the... 

As in the other methods, the modelless procedure visualizes the progressive emptying of the pore system, initially full up, by the stepwise reduction in relative pressure. At each step the value of additional core wall area which becomes exposed is calculated by means of the equation (see p. 170) ... 

Multiply unsaturated linolenic and linoleic acid residues make triglycerides more vulnerable to oxidative degradation than oleic acid which is relatively stable. It is therefore desirable to hydrogenate the most unsaturated residues selectively without production of large quantities of stearic (fully saturated) acid. The stepwise reduction of an unsaturated oil may be visualized as ... 

Reduction to Metal Powder. The metal powder is obtained from APT by stepwise reduction with carbon or hydrogen. The intermediate products are the yeUow oxide, WO blue oxide, (see Tungsten compounds) and brown oxide, WO2. Because carbon introduces impurities,... 

Because transition metals even in a finely-divided state do not readily combine with CO, various metal salts have been used to synthesize metal carbonyls. Metal salts almost always contain the metal in a higher oxidation state than the resulting carbonyl complex. Therefore, most metal carbonyls result from the reduction of the metal in the starting material. Such a process has been referred to as reductive carbonylation. Although detailed mechanistic studies ate lacking, the process probably proceeds through stepwise reduction of the metal with simultaneous coordination of CO (90). 

The homolog of epinephrine in this series is a potent vasoconstrictor. Reaction of 3,4-dimethoxypropiophenone with butyl nitrite leads to nitrosation at the a position (36). Stepwise reduction of the nitrosoketone leads to the amino alcohol (37). Removal of the methyl ether affords racemic 38. Resolution of this last followed by separation of the (-) isomer gives levonor-defrine (38). ... 

It is possible to titrate two substances by the same titrant provided that the standard potentials of the substances being titrated, and their oxidation or reduction products, differ by about 0.2 V. Stepwise titration curves are obtained in the titration of mixtures or of substances having several oxidation states. Thus the titration of a solution containing Cr(VI), Fe(III) and V(V) by an acid titanium(III) chloride solution is an example of such a mixture in the first step Cr(VI) is reduced to Cr(III) and V(V) to V(IV) in the second step Fe(III) is reduced to Fe(II) in the third step V(IV) is reduced to V(III) chromium is evaluated by difference of the volumes of titrant used in the first and third steps. Another example is the titration of a mixture of Fe(II) and V(IV) sulphates with Ce(IV) sulphate in dilute sulphuric acid in the first step Fe(II) is oxidised to Fe(III) and in the second jump V(IV) is oxidised to V(V) the latter change is accelerated by heating the solution after oxidation of the Fe(II) ion is complete. The titration of a substance having several oxidation states is exemplified by the stepwise reduction by acid chromium(II) chloride of Cu(II) ion to the Cu(I) state and then to the metal. 

Among several applications, Fe-based hydrogenases play a central role in the stepwise reduction of CO2 to methane. This process is accomplished through various types of Fe-hydrogenases however, in most of these enzymes, the active center is either a binuclear Fe-Fe- or an Ni-Fe-complex. Although the exact... 

It is necessary therefore to seek the cause of the induced air oxidation in the ClOJ-Cl system. The fact that, during the stepwise reduction of chlorate, chlorine oxide (CIO), which can easily react with molecular oxygen ... 

Meah Y, V Massey (2000) Old yellow enzyme stepwise reduction of nitroolefins and catalysis of acid-nitro tautomerization. Proc Natl Acad Sci USA 97 10733-10738. 

This behaviour was rationalised by a stepwise reduction mechanism, in which a high catalyst or KOH concentration gives a high hydride concentration and leads to the aniline formation and suppression of intermolecular reactions to the dimeric azo-compound. 

Similarly, Pd, Ag, and Pd-Ag nanoclusters on alumina have been prepared by the polyol method [230]. Dend-rimer encapsulated metal nanoclusters can be obtained by the thermal degradation of the organic dendrimers [368]. If salts of different metals are reduced one after the other in the presence of a support, core-shell type metallic particles are produced. In this case the presence of the support is vital for the success of the preparation. For example, the stepwise reduction of Cu and Pt salts in the presence of a conductive carbon support (Vulcan XC 72) generates copper nanoparticles (6-8 nm) that are coated with smaller particles of Pt (1-2 nm). This system has been found to be a powerful electrocatalyst which exhibits improved CO tolerance combined with high electrocatalytic efficiency. For details see Section 3.7 [53,369]. 

Figur 4.31 Sequential, isocratic elution using a stepwise reduction in solvent strength to identify a binary solvent of acceptable strength for elution of a five ca x>nent mixture. In this example the column holdup time was 1 min.

It has been reported that bimetallic nanoparticles with core/shell structure can be prepared by ultrasonic irradiation. Mizukoshi et al. reported the formation of bimetallic nanoparticles of Au core/Pd shell structure [42,43] from the sonochemical reduction of Au(III) and Pd(II), where the stepwise reduction of metal ions was observed to proceed during ultrasonic irradiation. That is, the reduction of Pd(II) started after the reduction of Au(III) finished. Vinodgopal et al. reported... 

Many anionic nucleophiles add to the carbyne carbon in cationic Fischer complexes, and these reactions can be used to synthesize carbene ligands unavailable by other routes. The stepwise reduction of a metal-carbon triple bond has been demonstrated (32) ... 

Sigman et al. [134] have described a bacterial method for measuring the isotopic composition of seawater nitrate at the natural-abundance level. The method is based on the analysis of nitrous oxide gas (N2O) produced quantitatively from nitrate by denitrifying bacteria. The classical denitrification pathway consists of the stepwise reduction of nitrate (NOp to nitrite (N02), nitric oxide (NO), nitrous oxide (N2O), and dinitrogen (N2) ... 

Sigma-bond metathesis at hypovalent metal centers Thermodynamically, reaction of H2 with a metal-carbon bond to produce new C—H and M—H bonds is a favorable process. If the metal has a lone pair available, a viable reaction pathway is initial oxidative addition of H2 to form a metal alkyl dihydride, followed by stepwise reductive elimination (the microscopic reverse of oxidative addition) of alkane. On the other hand, hypovalent complexes lack the... 

For comparison, the ITAM-derived 19-mer bidentate peptide inhibits with an IC50 of 30 nmol/1 [141]. Concluding, the chosen peptoid approach did not yield in the desired breakthrough for the design of useful SH2 domain inhibitors. Also in terms of stepwise reduction of the peptide character, no information for the subsequent design of next-generation analogues could be derived [141]. 

There have been many recent studies in support of this mechanistic approach. Stepwise reductive formation of Ag3+ and Ag4+ clusters has been followed using spectroscopic methods by Henglein [33], Reduction of copper (II) to colloidal Cu protected by cationic surfactants (NR4+) through the intermediate Cu+ prior to nucleation of the particles [36] as monitored by in situ x-ray absorption spectroscopy is another example. The seed-mediated synthesis also serves as evidence in support of this mechanism [38-41],... 

Polychloroethylenes follow a stepwise reductive cleavage mechanism involving c -Cl + e -Cl sequences (Figure 3.11), as expected from the resemblance between chlorine-carbon bonds in vinylic and aromatic positions. 

As illustrated in Figure 104 for [NiBr(triphos)] +, these complexes display the stepwise reductions Ni(II)/Ni(I)/Ni(0). The former is chemically and electrochemically reversible, whereas the latter is essentially irreversible.155... 

The reductive cleavage of iodobenzene and 3-methyliodobenzene was studied by cyclic voltammetry in both DMF and acetonitrile at 21 and 56 °C at different scan rates and has shown that there is a transition between stepwise and concerted mechanisms at lower scan rates. 1-Iodonaphthalene undergoes a stepwise reductive cleavage with mixed kinetic control by electron transfer and follow-up bond breaking, whatever the scan rate. ... 

Hilarides and others (1994) investigated the destruction of TCDD on artificially contaminated soils using °Co y radiation. It appeared that TCDD underwent stepwise reduction dechlorination from tetra- to tri-, then di- to chlorodioxin, and then to presumably nonchlorinated dioxins and phenols. The investigators discovered that the greatest amount of TCDD destruction (92%) occurred when soils were amended with 25% water and 2% nonionic surfactant [alkoxylated fatty alcohol (Plurafac RA-40)]. Replicate experiments conducted without the surfactant lowered the rate of TCDD destruction. 

Reduction of dibenzothiophene with sodium in liquid ammonia has been shown to be sensitive to the experimental methods employed however, the major product is usually 1,4-dihydrodibenzothiophene. 27 -28i The electrochemical reduction of dibenzothiophene in ethylene-diamine-lithium chloride solution has been shown to proceed via stepwise reduction of the aromatic nucleus followed by sulfur elimination. In contrast to the reduction of dibenzothiophene with sodium in liquid ammonia, lithium in ethylenediamine, or calcium hexamine in ether, electrolytic reduction produced no detectable thiophenol intermediates. Reduction of dibenzothiophene with calcium hexamine furnished o-cyclohexylthiophenol as the major product (77%). Polaro-graphic reduction of dibenzothiophene 5,5-dioxide has shown a four-electron transfer to occur corresponding to reduction of the sulfone group and a further site. ... 

The decomposition by the fungus, Trametes versicolor, of diatrizoate, iodi-pamide and related triiodinated benzoates was investigated by Rode et al. [121]. All compounds were degraded, albeit not completely, under iodide release. Isolation and identification of metabolites suggested stepwise reductive de-iodina-tions as initial transformation steps. 

If a decision is made to discontinue therapy with lamotrigine, a stepwise reduction of dose over 2 weeks or more (approximately 50% per week) is recommended unless safety concerns require a more rapid withdrawal (see Precautions). 

Therefore, Cjq was predicted to be a fairly electronegative molecule, being reducible up to the hexaanion [8]. Indeed, this was supported by very early investigations carried out with in solution, namely cyclic voltammetry studies, which showed its facile and stepwise reduction. In these first investigations, Cgg was reduced by two [9] and three [10] electrons. 

Fulleride anions are often more soluble, especially in more polar solvents, than the parent fullerenes. For example, in bulk electrolysis experiments with tetra-n-butylammonium perchlorate (TBACIO4) as supporting electrolyte, carried out in acetonitrile where Cjq is completely insoluble, fairly concentrated, dark red-brown solutions of 50 can be obtained [81]. Upon reoxidation, a quantitative deposition of a neutral Cjq film on the surface of a gold/quartz crystal working electrode takes place. This Cjq film can be stepwise reductively doped with TBA, leading to (Cjo )... 

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