Mechanisms of olefins

Double-bond migrations during hydrogenation of olefins are common and have a number of consequences (93). The extent of migration may be the key to success or failure. It is influenced importantly by the catalyst, substrate, and reaction environment. A consideration of mechanisms of olefin hydrogenation will provide a rationale for the influence of these variables. 

Carrick, W. L. The Mechanism of Olefin Polymerization by Ziegler-Natta Catalysts. VoL 12, pp. 65-86. 

In studying two-component polymerization catalysts, beginning with Feldman and Perry (161), a radioactive label was introduced into the growing polymer chain by quenching the polymerization with tritiated alcohols. The use of these quenching agents is based on the concept of the anionic coordination mechanism of olefin polymerization occurring... 

Figure 12.2 Mechanism of olefin hydrogenation by transition metal complexes.

The three theoretical studies presented above give somehow different conclusions regarding the detailed reaction mechanisms. The difference is apparently related to the different models used and different theoretical approaches employed in the calculations. In any case, the emerging overall picture is that the reaction mechanism of olefin hydroborations must be complicated. We would like to see more experimental work done in the future so that the theoretical results can be tested. In particular, it would be nice to evaluate experimentally the utility of the suggestion made by Ziegler and co-workers in the choice of the phosphine ligands in order to produce more pure product. 

Mechanism of Olefin Epoxidation by Transition Metal Peroxo Compounds... 

During the last three decades, peroxo compounds of early transition metals (TMs) in their highest oxidation state, like TiIV, Vv, MoVI, WV1, and Revn, attracted much interest due to their activity in oxygen transfer processes which are important for many chemical and biological applications. Olefin epoxidation is of particular significance since epoxides are key starting compounds for a large variety of chemicals and polymers [1]. Yet, details of the mechanism of olefin epoxidation by TM peroxides are still under discussion. 

Figure 3. Schematic representation of the TS structures of the various mechanisms of olefin epoxidatian.

The metallacyclobutane mechanism of olefin metathesis has been discussed in Sections 1.3 and 3.1.7. For metathesis of acetylenes carbyne complexes are generally required (Figure 3.44), and both heterogeneous and homogeneous catalytic systems have been developed for this purpose. 

Scheme 11.5 Four-step mechanism of olefin metathesis coordination, [2t-2] cycloaddition, [2+2] cycloreversion and de-coordination [4].

The first quantum-chemical investigation of the mechanism of olefin epoxidation in flnoroalcohols was carried out by Shaik et al. [54], In the absence of kinetic data, a monomolecular mode of activation by the fluorinated alcohols for aU reaction pathways was assnmed [54],... 

Figure 14.1 Mechanism of olefin free radical polymerization.

R.S. Disselkamp, K.M. Denslow, T.R. Hart, C.H.F. Peden Non-equilibrium Effects in the Hydrogenation-mediated Isomerization Mechanism of Olefins during Cavitating Ultrasound Processing, Catal Commun., in press (2006). R.S. Disselkamp, K.M. Judd, T.R. Hart, C.H.F. Peden, G.J. Posakony, L.J. 

Migration of organosilicon groups from metal to ligand is believed to be a key step in the mechanism of olefin hydrosilylation catalyzed by nickel-phosphine complexes (59), as shown in Scheme 1. (Substituents are omitted for clarity.)... 

In discussing the mechanism of eliminations over solids, the nomenclature which has been developed for homogeneous reactions will be used. Therefore the basic mechanisms of olefin formation have first to be outlined and their meaning in heterogeneous catalysis defined. 

However, the investigations of the mechanism of olefin and ether formation from alcohol (Sect. 2.2) revealed the importance of basic sites. It is feasible that, for esterification also, pairs of acidic and basic sites might be necessary. 

Oxidation of 2-Butene with Selenium Dioxide. The stoichiometry of the reaction of 2-butene with selenium dioxide shows that approximately 0.85 mole of l-acetoxy-2-butene plus 0.85 mole of bis(l-methyl-2-acetoxypropyl) selenide are produced per mole of selenium dioxide consumed. This suggests that, at least for this particular group of olefins, in the mechanism of olefin oxidation with selenium dioxide the formation of selenides should be considered as the final reduced state of the oxidant rather than elemental selenium. 

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