Titanium induced process

Another consequence of this surface sol-gel process on SBA-15 is the reduction of the surface silanol groups induced by the condensation reaction with titaniumbutoxide. The reaction, after hydrolysis, converts surface silanol functionality, (SiO)3SiOH, into Ti-OH functionality. Given the similar electronegativity of silicon (1.8) and titanium (1.7), the expected consequence of this modification in the solid state Si NMR is a decrease in the band and a corresponding increase in the Q band that is, the OTi(OH)3 and OSi(OH)3 ligands will cause equivalent NMR shift perturbations on the substituted silicon site. 

Various transition metals have been used in redox processes. For example, tandem sequences of cyclization have been initiated from malonate enolates by electron-transfer-induced oxidation with ferricenium ion Cp2pe+ (51) followed by cyclization and either radical or cationic termination (Scheme 41). ° Titanium, in the form of Cp2TiPh, has been used to initiate reductive radical cyclizations to give y- and 5-cyano esters in a 5- or 6-exo manner, respectively (Scheme 42). The Ti(III) reagent coordinates both to the C=0 and CN groups and cyclization proceeds irreversibly without formation of iminyl radical intermediates.The oxidation of benzylic and allylic alcohols in a two-phase system in the presence of r-butyl hydroperoxide, a copper catalyst, and a phase-transfer catalyst has been examined. The reactions were shown to proceed via a heterolytic mechanism however, the oxidations of related active methylene compounds (without the alcohol functionality) were determined to be free-radical processes. 

The lag between the time that nitinol, was first produced and the time it was used commercially in medical devices was due in part to the fear that nickel would leach from the metal and not be tolerable as a human implant. As it turns out, with a correct understanding of the surface electrochemistry and subsequent processing, a passivating surface layer can be induced by an anodizing process to form on the nitinol surface. It is comprised of titanium oxide approximately 20 mn thick. This layer actually acts as a barrier to prevent the electrochemical corrosion of the nitinol itself. Without an appreciation for the electrochemistry at its surface, nitinol would not be an FDA-approved biocompatible metal and an entire generation of medical devices would not have evolved. This is really a tribute to the understanding of surface electrochemistry within the context of implanted medical devices. 

Historically the most commonly used lithium intercalation compound was titanium disulphide, TiS2- This compound has a layered structure of covalently bound S-Ti-S stacks held together by weak van der Waals forces. Each stack is formed by a layer of titanium atoms between two layers of sulphur atoms in a hexagon ally close packed arrangement, Lithium ions can be readily intercalated between the stacks, and if the intercalation level x is maintained below unity, the process induces only a modest and reversible expansion along the c axis (Fig. 7.13). The electrochemical reaction of the Li/TiS2 couple... 

Interestingly, the titanium(IV) isopropoxide catalyzed process can still be highly diastereoselec-tivc28. In certain cases with more Lewis acidic catalysts (Cl, TiO-/-Pr or EtAlCl2) even acetalic oxygen in a homoallylic position can induce stereospecificity22. 

P-Keto esters and -keto amides, each substituted between the two carbonyl units with a 2-[2-(tri-methylsilyl)methyl] group, also undergo Lewis acid catalyzed, chelation-controlled cyclization. When titanium tetrachloride is used, only the product possessing a cis relationship between the hydroxy and ester (or amide) groups is product yields range from 65 to 88% (Table 8). While loss of stereochemistry in the product and equilibration of diastereomers could have occurred via a Lewis acid promoted retro aldol-aldol sequence, none was observed. Consequently, it is assumed that the reactions occur under kinetic, rather than thermodynamic, control. In contrast to the titanium tetrachloride promoted process, fluoride-induced cyclization produces a 2 1 mixture of diastereomeric products, and the nonchelating Lewis acid BF3-OEt2 leads to a 1 4.8 mixture of diastereomers. 

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