Oxygen reaction with metals

Phosphoms shows a range of oxidation states from —3 to +5 by virtue of its electronic configuration. Elemental P is oxidized easily by nonmetals such as oxygen, sulfur, and halides to form compounds such as 2 5 2 5 reduced upon reaction with metals to generate phosphides. The... 

Alkali metal A metal in Group 1 of the periodic table, 31 hydrogen reactions with, 542 oxygen reactions with, 543-544 reactions of, 541t, 552q water reactions with, 542... 

This overview is organized into several major sections. The first is a description of the cluster source, reactor, and the general mechanisms used to describe the reaction kinetics that will be studied. The next two sections describe the relatively simple reactions of hydrogen, nitrogen, methane, carbon monoxide, and oxygen reactions with a variety of metal clusters, followed by the more complicated dehydrogenation reactions of hydrocarbons with platinum clusters. The last section develops a model to rationalize the observed chemical behavior and describes several predictions that can be made from the model. 

The Importance of Reactions of Oxygen Bases with Metal Carbonyl Derivatives in Catalysis... 

The method of photosensitized oxygenation was successfully applied in the preparation of alcohols 265-270 from sylvestrene (264),207 and seems to be the most simple and successful method for the preparation of optically active rose oxides (272,273) from (+)- or (—)-citronellol C271).177 It may also be used for the preparation of certain organo-metallic hydroperoxides. Thus, the triphenyl-tin derivative of tri-methylethylene (274) undergoes a photosensitized oxygenation reaction with a rate similar to that of tetramethylethylene, giving rise to the hydroperoxides 275 and 276 219... 

This mechanism, involving a free radical R , is compatible with the allylic rearrangements found.250 The finding that t-butyl peresters labeled with ibO in the carbonyl oxygen gave ester with 50% of the label in each oxygen251 is in accord with a combination of R with the intermediate 19, in which the copper is ionically bound, so that the oxygens are essentially equivalent. Other evidence is that f-butoxy radicals have been trapped with dienes.252 Much less is known about the mechanisms of the reactions with metal acetates.253... 

At this point, you should recall and review numerous important items of information concerning the chemical properties of the metals, including the relative activity of metals the union of metals with oxygen reactions between metals and acids, water, and bases base-forming properties behavior as reducing agents and so forth. 

The stereochemical outcome of these electrophilic additions is consistent with a transition state in which the metal chelates the oxazolidinone carbonyl and the enolate oxygen. Reaction with an electrophile would, therefore, occur at the less hindered diastereotopic face of the (Z)-enolate, away from the shielding methyl groups of the auxiliary (Figure 24.6). Because both enantiomers of oxazolidinone 108 are equally available, the direction of the asymmetric induction can be controlled by proper choice of the absolute stereochemistry of the chiral auxiliary.106... 

A number of transition metals are now known147-156 to form stable dioxygen complexes, and many of these reactions are reversible. In the case of cobalt, numerous complexes have been shown to combine oxygen reversibly.157 158 Since cobalt compounds are also the most common catalysts for autoxidations, cobalt-oxygen complexes have often been implicated in chain initiation of liquid phase autoxidations. However, there is no unequivocal evidence for chain initiation of autoxidations via an oxygen activation mechanism. Theories are based on kinetic evidence alone, and many authors have failed to appreciate that conventional procedures for purifying substrate do not remove the last traces of alkyl hydroperoxides from many hydrocarbons. It is usually these trace amounts of alkyl hydroperoxide that are responsible for chain initiation during catalytic reaction with metal complexes. 

Ignition or explosive reaction with metals (e.g., aluminum, antimony powder, bismuth powder, brass, calcium powder, copper, germanium, iron, manganese, potassium, tin, vanadium powder). Reaction with some metals requires moist CI2 or heat. Ignites with diethyl zinc (on contact), polyisobutylene (at 130°), metal acetylides, metal carbides, metal hydrides (e.g., potassium hydride, sodium hydride, copper hydride), metal phosphides (e.g., copper(II) phosphide), methane + oxygen, hydrazine, hydroxylamine, calcium nitride, nonmetals (e.g., boron, active carbon, silicon, phosphoms), nonmetal hydrides (e.g., arsine, phosphine, silane), steel (above 200° or as low as 50° when impurities are present), sulfides (e.g., arsenic disulfide, boron trisulfide, mercuric sulfide), trialkyl boranes. 

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