Oxidation stochiometric reaction

In alkaline solution, hypochlorite oxidizes nitrite to nitrate with the rate expression (10) and stochiometric reaction (11). 

Following on from stochiometric iridium-based C-H functionalizations, iridium-catalyzed reactions have been developed and can be combined with oxidation chemistry to enable the selective functionalization of aromatics. Moreover, these reactions can be performed under solventless conditions (Equations (91) and (92)). ... 

There are several publications devoted to oxidative additions to dihydropyridines [337, 338, 339, 340, 341]. For instance, the addition of stochiometric amounts of iodine in a methanol solution of dihydropyridine 309 gives iodi-nated tetrahydropyrimidine 310 in a stereoselective manner [337]. The same result is obtained when the reaction is performed with AModosuccinimide (NIS) (Scheme 3.107). Interestingly, when the process is carried out in tetra-hydrofuran the incorporation of the succinimide moiety at position 2 yields 3-iodo-2-succinimidotetrahydropyridine 311. Using Af-bromosuccenimide, TV-chlorosuccenimide and 7V-fluoropyridinium trifluoromethanesulfonate produces 3-bromo-, 3-chloro- and 3 flouro-substituted pyridines [337]. 

The geometric structure of the intetface. Many catalytic reactions are surface sensitive and it is well known that the metal-support interactions are strongly textural and stochiometrically dependent [11,14]. Moreover, it is of particular interest to understand if the metal clusters introduce new active sites, where chemical reactions can occur on the oxide support. 

The theoretical oxygen demand (ThOD), is solely the oxygen needed on a stochiometric basis to oxidize the solvent completely, and is thus the worst possible effect, but may be useful if no laboratory results are available. In this book the values of ThOD do not include for the oxidation of the nitrogen where it exists in the solvent s molecule. This tends to be a slow reaction and seldom is represented in the five-day BOD test. 

Stahl and Sheldon have shown how oxidations can be driven by air as primary oxidant, or source of stochiometric oxidizing power. Like the catalysts in this subsection, biological oxidases are enzymes that use O2 but do not incorporate its O atoms into the substrate. For example, Pd(OAc)2-pyridine is active for alcohol oxidation, intramolecular hetero- and carbocyclization of alkenes, intermolecular O-C and C-C coupling reactions with alkenes, and oxidative C-C bond cleavage of tertiary alcohols. A pathway for alcohol oxidation is shown in Eq. 9.27. Normally a 4e process, reduction of O2 can be hard to couple with oxidation of the catalytic intermediates, processes that often proceed in 2e steps. In this case, intermediate rj -peroxo Pd(II) complexes can be formed from reaction of Pd(0) intermediates with O2, which thus acts as a 2e oxidant. 

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