Metal alkoxide compounds

Metal alkoxide compounds, frequently represented as M(OR)x, where M is a metal and R is an alkyl group, are the most common precursors in sol-gel CSD processes and are also frequently used in chelate processes.3-12,30-34 Groups such as OR, which are bound to a metal center, are frequently referred to as ligands. Alkoxide compounds, including commonly used alkoxides such as... 

Other reports confirm similar reaction of C02 with metal alkoxide compounds. Benzene solutions of the alkoxide compounds Ti(OBu")4, Zr(OBu")4, Zr(OEt)4, Nb(OEt)5, and Fe(OEt)3 were found to absorb carbon dioxide in various amounts (151). Only Zr(OBu")4 reacted with an amount approaching one equivalent per metal complex. The solution ir spectra indicate formation of coordinated organic carbonates. From this evidence, equilibrium formation of the species M(0R) 1(02C0R) under 1 atm of C02 is inferred. 

Group 2 metal alkoxide compounds are potentially suitable as CVD precursors, especially because hydrolysis and subsequent thermally induced dehydration are likely to lead to complete removal of the supporting ligands. There are examples of Group 2 metal alkoxide compounds that are claimed to have suitable volatility for CVD, but to our knowledge these have not been used successfully. However, Group 2 metal alkoxide compounds have found widespread application in solution routes to metal oxide materials, an area that has been reviewed.1... 

The chemical synthesis of metal oxide nanocrystals based on hydrolysis falls into two major groups hydrolysis of metal alkoxides hydrolysis of metal halides, and other inorganic salts. Metal alkoxide compounds are defined as compounds that have metal-oxygen-carbon bonds. Si(OC2H5)4 (tetraethyl orthosUicate or TEOS), for instance, is an alkoxide compound. This class of compound is highly reactive with water. Because the hydroxyl ion (OH ) becomes bonded to the metal of the organic precursor, this reaction is called hydrolysis. Equation (50) shows a typical hydrolytic reaction of an alkoxide compound [100] ... 

Enolate Initiators. In principle, ester enolate anions should represent the ideal initiators for anionic polymeri2ation of alkyl methacrylates. Although general procedures have been developed for the preparation of a variety of alkaU metal enolate salts, many of these compounds are unstable except at low temperatures (67,102,103). Usehil initiating systems for acrylate polymeri2ation have been prepared from complexes of ester enolates with alkak metal alkoxides (104,105). 

In anionic polymerization the reaction is initiated by a strong base, eg, a metal hydride, alkah metal alkoxide, organometaHic compounds, or hydroxides, to form a lactamate ... 

Metal alkoxides are compounds in which a metal is attached to one or more alkyl groups by an oxygen atom. Alkoxides are derived from alcohols by the replacement of the hydroxyl hydrogen by metal. 

Stmctures are highly varied among the transition metals. The titanium atom in titanium tetraethoxide has the coordination number 6 (Fig. 1). The corresponding zirconium compound, with coordination number 8, has a different stmcture (Fig. 2). Metal alkoxides are colored when the corresponding metal ions are colored, otherwise they are not. 

Many metal alkoxides decompose at higher temperatures to lower valency compounds, in some cases to metal. 

Double Alkoxides. Complex double alkoxides are formed when a solution of an alkaU or alkaline earth metal alkoxide is added to a solution of an alkoxide of aluminum, titanium, or tirconium and a series of such compounds have been prepared (44). 

Various inorganic esters have been claimed as coupling agents for reinforced plastics, including aminobenzyl phosphonates, dicetylisopropylborate, alkoxy compounds of aluminum, zirconium and titanium, zircoaluminates, and numerous substituted titanates [1]. These metal alkoxides could function in a similar manner to the orthosilicates by reacting with hydroxylated substrates. Like the simple orthosilicates such as tetraethyl orthosilicate (TEOS), it is less evident how an-... 

Zinc phthalocyanine (PcZn) is prepared from phthalonitrile in solvents with a boiling point higher than 200 C, e.g. quinoline277,278 or 1-bromonaphthalene,137 or without solvent in a melt of phthalonitrile.83,116 The zinc compound normally used is zinc(ll) acetate or zinc powder. The reaction of zinc(II) acetate with phthalic acid anhydride, urea and ammonium mo-lybdate(VI) is also successful.262 The metal insertion into a metal-free phthalocyanine is carried out in an alcohol (e.g.. butan-l-ol).127,141,290 This reaction can be catalyzed by an alkali metal alkoxide.112,129... 

DNA polymerases, 5, 1007 Trans effect, 1,16, 26, 315 metal complexes, 2, 705, palladium(II) amine complexes, 5, 1115 platinum complexes, 5, 353, 493 six-coordinate compounds. 1, 49 T ransestcrification metal alkoxide synthesis, 2, 340 Transferases zinc, S, 1002... 

A previous method [1] of preparing 3,3-dimethylbutyne by dehydrochlorination of the title compound in a sodium hydroxide melt is difficult to control and hazardous on the large scale. Use of potassium ferf-butoxide as base in DMSO is a high-yielding, safe and convenient alternative method of preparation of the alkyne [2], See Dimethyl sulfoxide Metal alkoxides See other HALOALKANES... 

Metal alkoxides undergo alkoxide exchange with alcoholic compounds such as alcohols, hydro-xamic acids, and alkyl hydroperoxides. Alkyl hydroperoxides themselves do not epoxidize olefins. However, hydroperoxides coordinated to a metal ion are activated by coordination of the distal oxygen (O2) and undergo epoxidation (Scheme 1). When the olefin is an allylic alcohol, both hydroperoxide and olefin are coordinated to the metal ion and the epoxidation occurs swiftly in an intramolecular manner.22 Thus, the epoxidation of an allylic alcohol proceeds selectively in the presence of an isolated olefin.23,24 In this metal-mediated epoxidation of allylic alcohols, some alkoxide(s) (—OR) do not participate in the epoxidation. Therefore, if such bystander alkoxide(s) are replaced with optically active ones, the epoxidation is expected to be enantioselective. Indeed, Yamada et al.25 and Sharp less et al.26 independently reported the epoxidation of allylic alcohols using Mo02(acac)2 modified with V-methyl-ephedrine and VO (acac)2 modified with an optically active hydroxamic acid as the catalyst, respectively, albeit with modest enantioselectivity. 

For polymeric CSD processes, three classes of metal organic (metallo-organic) compounds are used most often as starting reagents metal alkoxides, metal carboxylates, and metal beta-diketonates. These species differ in their solubility and reactivity, as well as their tendency to react with one another, all of which are factors that may influence starting reagent selection. Representative structures of these classes of precursors are illustrated in Fig. 2.2.8... 

Most often in these processes, compounds such as acetic acid, acetylacetone (acac, 2,4-pentanedione), or amine compounds are employed, since these compounds readily react with alkoxides.4M877 A typical reaction involves the formation of new chemical species that (hopefully) possess physical and chemical characteristics that are more attractive in terms of solution stability and film formation behavior. An example reaction between a metal alkoxide and acetic acid is shown below ... 

In some instances, this approach has proven successful, with comparatively low crystallization temperatures being observed. For example, Eichorst and Payne in the synthesis of LiNb03 noted crystallization temperatures of 400-500 °C for a mixed-metal alkoxide precursor.111 In other instances, these attempts have proven less successful. Numerous attempts have been made to synthesize Pb-Zr and Pb-Ti precursors, each with the 1 1 cation stoichiometry of the desired PbZr03 and PbTi03 compounds.83,84 Unfortunately, 1 1 stoichiometric ratio compounds have not always been obtained, with crystalline compounds of other stoichiometries precipitating from the solution, as illustrated in Fig. 2.11.83 This figure shows the crystal structure of PbTi2[p(4)—... 

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