Oxidative insertion oxidizing agent

Strong oxidizing agents such as m-chloroperbenzoic (MCPBA) acid also react with polysilanes, to insert oxygen atoms between the silicons (17)... 

Bivalent tin compounds can easily be transformed to fourvalent tin compounds by oxidizing agents. Mechanistically, this reaction can be understood as an insertion of a six-electron system into a two-electron bond, resulting in a tetrahedrally tetra-coordinated tin atom. This process is often also regarded as an oxidative addition, a distinction being made between additions to a-bonds and to it-bonds. 

All these reactions are promoted by Pd(II) species, and can be stoichiometric (Eq. 10) or catalytic (Eqs. 11-13, in the presence of Cu(II) salts or other oxidizing agents). 3-Chloropropionyl chloride from ethylene is conceivably formed through PdCl2 addition to the double bond followed by CO insertion and reductive elimination (Scheme 2). 

The oxidation of organic substances by cyclic peroxides has been intensively studied over the last decades , from both the synthetic and mechanistic points of view. The earliest mechanistic studies have been carried out with cyclic peroxides such as phthaloyl peroxide , and more recently with a-methylene S-peroxy lactones and 1,2-dioxetanes . During the last 20 years, the dioxiranes (remarkable three-membered-ring cyclic peroxides) have acquired invaluable importance as powerful and mild oxidants, especially the epoxidation of electron-rich as well as electron-poor alkenes, heteroatom oxidation and CH insertions into alkanes (cf. the chapter by Adam and Zhao in this volume). The broad scope and general applicability of dioxiranes has rendered them as indispensable oxidizing agents in synthetic chemistry this is amply manifested by their intensive use, most prominently in the oxyfunctionalization of olefinic substrates. 

Polysilanes are chemically inert to air and water at ordinary temperature, but their reactivity increases in solvent. In a solvent such as tetrahydrofuran, degradation of the Si—Si backbone by strong bases is quite rapid. Strong oxidizing agents like /77-chloroperbenzoic acid insert oxygen atoms between the silicons to produce Si—O—Si linkages in the backbone (120). 

As an alternative to the mechanism above, it is possible that the reaction outlined in Eq. (49) proceeds by way of an oxidative-promoted insertion, in which a 17-electron alkyl carbonyl is formed which then rapidly undergoes insertion to produce an acyl complex. This redox-promoted reaction appears to occur in a rather large number of cases involving the action of metal or halogen oxidizing agents on metal alkyl carbonyls [Eq. (50)] (Ref. 221, and... 

The polymerization of aniline in the galleries of layered HNbMoOe was also reported by Byeon et al. Anihne was first inserted into the structure via an acid-base reaction to produce (anihnium)xNbMo06, which upon treatment with FeCl3 as an oxidizing agent resulted in the formation of (PANl)xNbMo06 [76]. 

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