Stille coupling basic principles

The same plasma polymer deposited in a closed-system reactor has a graded elemental composition with a carbon-rich top surface, and the oligomer content is much lower [10], both of which increase the level of adhesion. The adhesion of the same water-borne primer is excellent and survives 8 h immersion in boiling water. When this surface is treated with O2 plasma, the adhesion does not survive 1 h of boiling, while the dry tape test still remains at the level of 5. The water-sensitivity of adhesion depends on the chemical nature of the top surface as depicted by XPS data shown in Figure 28.12. Water-insensitive tenacious adhesion, coupled with good transport barrier characteristics, provides excellent corrosion protection, as supported by experimental data [1-4], and constitutes the basic principle for the barrier-adhesion approach. 

The most intense investigations were carried out in the development of catalysts and in studies of the reaction mechanisms. To date there are at least six mechanistic proposals for the reaction pathway of the dehydro-coupling, which have been reviewed by Gauvin et al. [77] two for catalysis by later transition metal complexes, and four for catalysis by group 4 metallocenes. Although the mechanism is still under discussion, the basic principle can be depicted in Scheme 6 [78a-ej. 

In principle, three basically different types of reaction modes are applied for cross-coupling reactions of allenes. First, cross-couplings of allenes with suitable halogen or metal substituents at one of the sp2-hybridized carbons furnish products still bearing the intact cumulene it-system. On this basis, numerous reactions for conversions of precursor 1 or 3 into substituted allenes 2 have been developed (Schemes 14.1 and 14.2). 

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