Oxygen , insertion reactions with

Despite the fact that a concerted oxygen insertion reaction appeared to be in complete agreement with existing experimental studies, Minisci and his group strongly advocated a... 

Metal Hydrides. It is likely that the reduction of aldehydes to alcohols by cobalt hydrocarbonyl (27) is an example of a carbonyl insertion reaction with a metal hydride. It is not clear which way the hydrocarbonyl adds to the carbonyl groups —whether it forms a cobalt-carbon bond (2), or a cobalt-oxygen bond (90). 

The mechanism of oxidation of alkanes with dimethyldioxirane has been examined by measurement of the primary kinetic isotope effect for the oxidation of cyclohexane and methylcyclohexane in solution and in the gas phase. These experiments indicated that the major products (cyclohexanol and methylcyclohexanol) are probably formed via an electrophilic oxygen-insertion reaction while minor by-products may arise from radical reactions.90... 

The chemical reactivity most associated with dioxiranes is the electrophilic transfer of oxygen to electron-rich substrates (e.g., epoxidation, N-oxidation) as well as oxygen insertion reactions into unactivated C-H bonds. The reactivity-selectivity relationships among these types of reactions has been examined in depth by Curci. The reaction kinetics are dependent upon a variety of factors, including electron-donor power of the substrate, electrophilicity of the dioxirane, and steric influences (95PAC811]. 

Heterocumulenes undergo insertion reactions with numerous substrates. In general, carbodiimides react faster than isocyanates and isothiocyanates, in that order. Insertions of carbodiimides into metal-hydrogen, metal-halogen, metal-mitrogen, metal-oxygen and metal-sulfur bonds are reported. Also insertions of carbodiimides into carbon-hydrogen bonds are known. 

Similar carbene insertion reactions with ethers are also very well known. Apart from direct C-H insertion, attack on oxygen can occur to form a very reactive dialkyloxonium methylide. ... 

A further requirement for the high selectivity to maleic anhydride from n-butane is the need for a correct sequence of oxidehydrogenation and oxygen insertion reactions. In the oxidation of n-butane the olefinic-like intermediate must be quickly oxidehydrogenated to an adsorbed dienic-like compound in order to favour the selective pathway towards maleic anhydride. In fact, this reaction may occur concurrently with the oxidation of allylic carbon atoms, with formation of aldehydes and acids which can also be precursors of carbon oxides. Thus, the selectivity to maleic anhydride depends on the relative rates of hydrogen abstraction and oxygen insertion. This property can be considered as typical of the vanadyl pyrophosphate for instance, in the case of the V/Mo/0 system the rate of oxygen insertion... 

The Baeyer-Villiger oxidation is an oxygen insertion reaction whereby an aldehyde, cyclic or acyclic ketone 1 is treated with a suitable oxidant, e.g., an organic peracid 3, to form the corresponding formate, lactone or ester 2. The oxidation takes place in two discrete steps (1) the attack of the peroxide on the carbonyl to provide the Criegee intermediate, followed by (2) rearrangement to the product ester. 

Oxygen insertion reactions of benzylamines with copper acetate in acetonitrile afford benzaldehyde and N-substituted amides. 

One-Atom Insertions. Siliranes also undergo one-atom insertion reactions with elemental sulfur, oxygen, or selenium. Similarly, the insertion of aryl or alkyl isocyanates provides iminosi-lacyclobutanes in high yield as single stereoisomers (eq 7). The reaction proceeds with the retention of silacyclopropane configuration and the insertion occurs at the more substituted C-Si bond when unsymmetrical siliranes are employed, similar to the regios-electivity observed for aldehydes and formamides. 

Oxygen,—[Os(H)(NO)a(PPh3)a]+ reacts with oxygen to form [Os(OH)-(NO)2(PPh3)2]+, apparently by an insertion reaction, with the consequent hydroperoxo-intermediate [Os(OOH)(NO)a(PPhs)2]+, for which there is a precedent in the chemistry of the [Co(H)(CN)5] - anion. A preliminary communication concerning the insertion of oxygen into the cobalt-carbon bond of cobaloximes (29) to produce (30), wherein R = H, Me, or OH and... 

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