Oxygen Insertion Reaction

A large amount of the work on palladium isocyanide complexes has been mentioned earlier, in discussions on insertion reactions 30,74,108,169,170) and on addition reactions of coordinated isocyanides 25, 33, 34, 49) the reactions of [Pd(CNBu )2] with oxygen 107) and with various olefins 29, 110) were noted. 

A novel potentially useful route for the synthesis of metallo-silanols is based on the reaction of metallohydridosilanes with 1,1-dimethyldioxirane [7,8] resulting in the insertion of oxygen into the Si-H bond. This procedure is supplementary to the hydrolysis route, since, in addition to the transformation of the "normal" ferrio-hydridosilanes 9a,b to the silanols 10a,b, it guarantees the formation of chiral 10c, not available by hydrolysis, from "electron rich" phosphine iron fragment substituted 9c (Eq. (2)). 

The oxygen insertion reaction can be extended to tungsten-hydridosilanes, which are noteworthy in that reaction (2) not only affords the silanol 12a, but also the double and even triple oxygenation products 12b,c starting from Cp (OC)2(Me3P)W-SiRH2 (R = H, Me) (11a,b). 

The S02 molecule has unshared pairs of electrons on both the sulfur and oxygen atoms. As a result, it forms numerous complexes with transitions metals in which it is known to attach in several ways. These include bonding through the sulfur atom, through an oxygen atom, by both oxygen atoms, and various bridging schemes. In most cases, the complexes involve soft metals in low oxidation states. Another important reaction of sulfur dioxide is known as the insertion reaction, in which it is placed... 

Suggestive evidence for the protonation of diphenylcarbene was uncovered in 1963.10 Photolysis of diphenyldiazomethane in a methanolic solution of lithium azide produced benzhydryl methyl ether and benzhydryl azide in virtually the same ratio as that obtained by solvolysis of benzhydryl chloride. These results pointed to the diphenylcarbenium ion as an intermediate in the reaction of diphenylcarbene with methanol (Scheme 3). However, many researchers preferred to explain the O-H insertion reactions of diarylcarbenes in terms of electrophilic attack at oxygen (ylide mechanism),11 until the intervention of car-bocations was demonstrated by time-resolved spectroscopy (see Section III).12... 

The major use of H202 as an oxidant arises from its ability to insert an oxygen atom in an organic molecule (alkene, alkane, aromatic hydrocarbon, etc.) in the presence of some catalysts. In reactions using H202 as an oxidant, the type of... 

The reaction between ketones and peracids such as perbenzoic acid or peracetic acid, provides esters. (Eq. (7)). The overall result is the insertion of oxygen . This... 

The mechanism of this one-pot reaction is proposed to be as follows (Figure 4.3) firstly, a chiral alkoxide ethylzinc is prepared from diethylzinc and the chiral alcohol with the evolution of a gas, which is probably ethane (I). The chiral ethylperoxyzinc alkoxide is formed by insertion of oxygen into the carbon zinc... 

Metal-oxygen bond, 27 195, 196 insertion reactions, 28 136-141 strength and selectivity, oxidative dehydrogenation of alkanes, 40 26-28... 

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... 

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