Oxygen, reaction with nickel

The oxygen reaction with sodium erythorbate is catalyzed by traces of nickel, copper, or iron in solution, so stainless steel or plastic stor-... 

This group is prepared by the reaction of the anion of 9-hydroxyanthracene and the tosylate of an alcohol. Since the formation of this group requires an S 2 displacement on the alcohol to be protected, it is best suited for primaiy alcohols. It is cleaved by a novel singlet oxygen reaction followed by reduction of the endo-peroxide with hydrogen and Raney nickel. 

They found that the order for the M—0 stretching modes (M—0 force constants) was (02)Pd(02) > Pd(Oj) and (02)Ni(02) > Ni(02), and since the 0-0 force constant increased as the M-0 force constant decreased, reversibility could not be equated with shorter 0—0 bond length. To test the proposed isosceles model they predicted the various absorptions that would be expected on the basis of the symmetrical structure (a) and unsymmetrical structure (c), Fig. 8. If the isotopic ratio of 0 0 is 1 1, then three bands would be expected for structure (a), with relative intensities 1 2 1, and four bands would be expected for structure (c), with relative intensities 1 1 1 1, the two oxygen atoms now being in different environments. These workers 189) then obtained the IR spectrum for the cocondensation product from the reaction between nickel and O2 (4.2—10°K), in isotopic ratio 0 =1 1, and found three bands with relative inten-... 

The family of poly(pyrazol-l-yl)borates has been widely used as supporting ligands in nickel coordination chemistry.556,557 Complex (191) is an example, where unusual cysteine coordination is achieved at a tris(pyrazolylborate)nickel(II) template.601 (191) undergoes rapid reaction with molecular oxygen to presumably form a sulfinate. 

It is postulated that the mechanism of the silane-mediated reaction involves silane oxidative addition to nickel(O) followed by diene hydrometallation to afford the nickel -jr-allyl complex A-16. Insertion of the appendant aldehyde provides the nickel alkoxide B-12, which upon oxygen-silicon reductive elimination affords the silyl protected product 71c along with nickel(O). Silane oxidative addition to nickel(O) closes the catalytic cycle. In contrast, the Bu 2Al(acac)-mediated reaction is believed to involve a pathway initiated by oxidative coupling of the diene and... 

Nickel oxide, NiO, which adopts the sodium chloride structure (Fig. 1.14), can readily be made slightly oxygen rich, and, because the solid then contains more oxygen than nickel, the crystal must also contain a population of point defects. This situation can formally be considered as a reaction of oxygen gas with stoichiometric NiO, and the simplest assumption is to suppose that the extra oxygen extends the crystal by adding extra oxygen sites. Atoms are added as neutral atoms, and... 

It is presently thought that the most obvious reason for the changed properties upon conversion from the unready to the ready state and then to the active state is the removal of the bound oxygen species (e.g. by reduction to OH, subsequent protonation to H2O and removal of this molecule from the active site). As indicated above, reduction causes a slow Niy-S Ni -S transition. It has been shown with the D. gigas enzyme (De Facey et al. 1997) that at 40°C and the appropriate redox potential, the species with the v(CO) of 1,914cm (Ni -S in our scheme) prevails at high pH, whereas a species with v(CO) at 1,934 cm (Nig-S) is the major form at low pH. It could well be that protonation of an OH bound to nickel in the Ni -S state forms a water molecule, which then leaves the active site (at 40°C, but not at 2°C see also Section 5.7), whereafter the site becomes accessible for a rapid reaction with H2. 

Electrochemically generated nickei(lll) oxide, deposited onto a nickel plate, is generally useful for the oxidation of alcohols in aqueous alkali [49]. The immersion of nickel in aqueous alkali results in the formation of a surface layer of nickel(ll) oxide which undergoes reversible electrochemical oxidation to form nickel(lll) oxide with a current maximum in cyclic voltammetry at 1.13 V vj. see, observed before the evolution of oxygen occurs [50]. This electrochemical step is fast and oxidation at a prepared oxide film, of an alcohol in solution, is governed by the rate of the chemical reaction between nickel oxide and the substrate [51]. When the film thickness is increased to about 0.1 pm, the oxidation rate of organic species increases to a rate that is fairly indifferent to further increases in the film thickness. This is probably due to an initial increase in the surface area of the electrode [52], In laboratory scale experiments, the nickel oxide electrode layer is prepared by prior electrolysis of nickel sulphate at a nickel anode [53]. It is used in an undivided cell with a stainless steel cathode and an alkaline electrolyte. 

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