Rearrangement or isomerization reactions

Abstract In this chapter, nanocluster catalyzed modifications of organic and silicon based polymers are described. The tailoring of the polymeric tanplates was carried out under mild conditions and led to hybrid polymers in quantitative yields. Detailed characterization studies indicated that the integrity of the polymeric templates was not compromised during the functionalization process. The nanoparticle catalysis was found to be quite effective and highly selective, hi most cases exclusive 6-hydrosilylation products were obtained without any rearrangement or isomerization reactions. Detailed characterization and property profiling of the new hybrid polymers is also presented. 

In rearrangement or isomerization reactions, one has coupling of a set of discrete initial states i> to a quasi-continuous but still discrete set of final states f>, as shown in equation (39). 

Rearrangement or isomerization reactions proceed typically at carbocations or other electron-deficient positions of a molecule. In rearrangement reactions the substrate stabilizes itself by rearranging its structure without changing the number and type of its atoms. Thus, rearrangement reactions proceed without addition/release of molecules other than substrate and product. Rearrangement reactions of technical importance are the isomerization of linear alkanes to branched alkanes (important to increase the quality of fuels) and the rearrangement of cyclohexanone oxime to e-caprolactam (Scheme 2.2.4). 

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