Metal-alkyl Lewis base interaction

Since the metal-alkene association preceding the peroxymetalation reaction in mechanism (B) is a pure Lewis acid/Lewis base interaction, it would be expected that compounds having alkylperoxy groups bonded to a Lewis acid center should be active for the epoxidation of alkenes. This is indeed found for boron compounds, which are active as catalysts for the epoxidation of alkenes by alkyl hydroperoxides.246,247 Isolated boron tris(alkyl peroxides), B(OOR)3, have been shown to epoxidize alkenes stoichiometrically, presumably through alkylperoxyboration of the double bond (equation 76).248... 

Although the first bis(iminophosphorano)methanides were reported by Elsevier,15 the first structurally characterised examples were reported by Cavell.16 Solvent-free 1 and 2 were prepared from the reaction between the parent methane and lithium or sodium bis(trimethylsilyl)amides in aromatic solvents. By avoiding Lewis base solvents such as ethers, dimeric complexes were isolated. Treatment with excess quantities of alkali metal amide did not effect a second deprotonation, even under reflux conditions over days, which was attributed to the less basic nature of amides compared to alkyls (see section 3.2 below). In addition to the expected methanide-alkali metal bonds, methine C H — Li interactions were observed in 1 in the solid state but the analogous C-H — Na interactions appeared to be weak in 2. 

It is well known that in conventional catalyst systems a chemical interaction between the catalyst and the metal-alkyl takes place, which essentially leads to a variation of the transition metal oxidation state. This is likewise true with MgCl2 catalysts however, in this case there are many more possible reactions, given the greater complexity of the system. Thus, besides modifying the Ti valence, the metal-alkyl may interact with the Lewis base incorporated in the catalyst. The Lewis base added to the cocatalyst can, in turn, interact both with the support and with the TiCl4, as can the byproducts originating from the reaction between Al-alkyl and Lewis base. The situation appears to be quite complex. However, detailed knowledge about these processes is absolutely necessary for any attempt to rationalize the polymerization behavior of these catalytic systems. 

Some other contributions of organometallic compounds to fundamental research are (a) the detection of free alkyl radicals by the pyrolysis of lead alkyls (b) the classification of hydrocarbon acidity via organoalkali compounds (c) the study of Lewis acid-base interactions with Group III alkyls (d) the development of the concept of electron-deficient compounds by the study of metal alkyls (e) the discovery of stereospecific olefin polymerization and (f) the investigation of nucleophilic additions to unsaturated organic compounds via reactive metal alkyls. 

Mg-Al mixed oxides obtained by thermal decomposition of anionic clays of hydrotalcite structure, present acidic or basic surface properties depending on their chemical composition [1]. These materials contain the metal components in close interaction thereby promoting bifunctional reactions that are catalyzed by Bronsted base-Lewis acid pairs. Among others, hydrotalcite-derived mixed oxides promote aldol condensations [2], alkylations [3] and alcohol eliminations reactions [1]. In particular, we have reported that Mg-Al mixed oxides efficiently catalyze the gas-phase self-condensation of acetone to a,P-unsaturated ketones such as mesityl oxides and isophorone [4]. Unfortunately, in coupling reactions like aldol condensations, basic catalysts are often deactivated either by the presence of byproducts such as water in the gas phase or by coke build up through secondary side reactions. Deactivation has traditionally limited the potential of solid basic catalysts to replace environmentally problematic and corrosive liquid bases. However, few works in the literature deal with the deactivation of solid bases under reaction conditions. Studies relating the concerted and sequential pathways required in the deactivation mechanism with the acid-base properties of the catalyst surface are specially lacking. 

Likewise, the number of available surfactants (Lewis bases) are also limited, since not all of them have available orbitals to form molecular orbitals with Lewis acid TM centers [74,76,82]. Typical surfactants used in the LAT method are alkyl phosphates and alkyl amines [72,74,76,82]. The second major drawback is the thermal stability of the formed mesostructure. Due to the strong S-I interaction, conventional solvent extraction methods are not enough to remove surfactant from mesostructured TM oxides to form mesoporous oxide materials. In addition, low metal to surfactant ratios ( 1) and essentially high temperature treatments (>500 °C) to remove hydrophobic alkyl chains, which make these materials thermally unstable. 

The approach and insertion of an olefin molecule may or may not pass through a local minimum or coordination complex (first in brackets in eq. 16) recent theoretical work (128) indicates that the well, if it indeed exists, is very shallow. The insertion of the new molecule into the growing chain is represented in equation 13 as a structure intermediate between reactants and products. The mechanism for this apparently concerted reaction does not involve the participation of metal-based electrons, and can be considered to be a Lewis acid-assisted anionic attack of the zirconium alkyl (ie, the polymer chain) upon one end of a carbon-carbon double bond. The concept of this reaction pre-dates metallocene study, and is merely a variant of the Cossee-Arlman mechanism (129) routinely invoked in Ziegler-Natta polymerization. Computational studies indicate (130) that an a-agostic interaction (131) provides much needed stabilization during the process of insertion. 

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