Organometallic reactivity, increased

The reactivity of organometallic compounds increases with the percent ionic character of the C-M bond. 

It might be noted also that either model is capable of explaining the irregular order 1° < 2° > 3° for reactivity in cyclization (see Section 11,D,6). In either case, one methyl group on Cc may occupy a conformation in which it is fairly well out of the way, allowing the electronic destabilization of the organometallic to produce a reactivity increase. However, if there are two methyls on C , one must be in a position of substantial steric congestion. 

The slow development of heavy alkali organometallic chemistry is due to high reactivity, as rationalized by the increase of polar character of the metal-ligand bond due to the reduced polarizing ability of the metals. The increase in ionic character on descending the group of alkali metals is clearly demonstrated by the increase in ionic radii with Li+(0.69A), Na+(0.97A), K+(1.33A), Rb+(1.47A), and Cs+(1.67A), resulting in a radius of Cs+ that is more than double of that of Li+. 

The rate also decreases with an increase in the chain length of the alkene molecule (hex-l-ene > oct-1-ene > dodec-l-ene). Although the latter phenomenon is attributed mainly to diffusion constraints for longer molecules in the MFI pores, the former (enhanced reactivity of terminal alkenes) is interesting, especially because the reactivity in epoxidations by organometallic complexes in solution is usually determined by the electron density at the double bond, which increases with alkyl substitution. On this basis, hex-3-ene and hex-2-ene would be expected to be more reactive than the terminal alkene hex-l-ene. The reverse sequence shown in Table XIV is a consequence of the steric hindrance in the neighborhood of the double bond, which hinders adsorption on the electrophilic oxo-titanium species on the surface. This observation highlights the fact that in reactions catalyzed by solids, adsorption constraints are superimposed on the inherent reactivity features of the chemical reaction as well as the diffiisional constraints. 

All these advances have resulted not only in increases in resolution but have also alleviated the detection problems to a considerable extent. As a result, the last decade has seen a dramatic growth in 15N- and 170-NMR spectroscopy as a versatile method for studying molecular structure, both in isotropic (liquid) and anisotropic (solid) phases. Studies at a natural abundance level of the nucleides are now commonplace. The scope of chemical applications extends from inorganic, organometallic and organic chemistry to biochemistry and molecular biology, and includes the study of reactive intermediates, biopolymers and enzyme-inhibitor complexes. 

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