Metal alkoxides reactions with carboxylic acids

The reactions of metal alkoxides with carboxylic acids and acid anhydrides can be represented by Eqs (2.231) and (2.232) ... 

Rai and Mehrotra later showed that the reaction of Al(OBu >3 with carboxylic acids yields the tricarboxylates more readily, as in this case the intermediate product A1(OBu )(OOCR)2 is monomeric and continues to react in a facile manner with the third mole of carboxylic acids. In fact the reactions of metal alkoxides with carboxylic acids are facilitated thermodynamically since the carboxylate moiety tends to bind the metal in a bidentate mode, thus ... 

The chemical properties of heterometallic alkoxides are in general similar to their homometal counterparts (i) hydrolysis, (ii) alcoholysis, (iii) trans-esterification reactions, (iv) reactivity with carboxylic acids and enolic forms of chelating ligands such as /3-diketones/j6-ketoesters. The hydrolytic reactions are now widely employed for the preparation of homogeneous mixed metal-oxide ceramic materials and the rest have found wide applications for the synthesis of a variety of novel metallo-organic derivatives (sometimes unique), which are not often available through any other synthetic route. ... 

Zirconium and hafnium tetraalkoxides are highly reactive compounds. They react with water, alcohols, silanols, hydrogen halides, acetyl halides, certain Lewis bases, aryl isocyanates and other metal alkoxides. With chelating hydroxylic compounds HL, such as j8-diketones, carboxylic acids and Schiff bases, they give complexes of the type ML (OR)4 these reactions are discussed in the sections dealing with the chelating ligand. 

The interaction of the metal alkoxides with the salts of carboxylic acids or with p-diketonates of other metals is especially attractive for the synthesis of bimetallic molecular precursors in the cases, when the preparation of the alkoxide of the other metal is somehow hindered or it is insoluble or irreactive under the conditions applied. This method has been widely used for the sol-gel preparation of HTSC materials (because of low solubility and reactivity of Cu(OR)2) and lead-containing ferroelectrics (in the view of difficult synthesis and low stability of Pb(OR)2). It should be mentioned that the reaction between a metal alkoxide and a functional derivative does far not always lead to the formation of a mixed-ligand bimetallic complex ... 

In [1677] complex alkoxides and alkoxide-carboxylates were compared as precursors for preparation ofBST films. In contrast to the introduction of alkaline earth carboxylates in the form of preliminary isolated salts, in this work metal alkoxide solution in methoxyethanol containing titanium and alkaline-earth metal was modified by addition of 2-ethylhexanoic acid with subsequent slow distilling off the solvent and repeated dilutions with fresh portions of methoxyethanol. During the distillation process, part of the alkoxide groups are substituted by the 2-ethylhexanoate ligands. The exchange reaction of Ti(OPr )4 with acid was studied in different solvents, and it was demonstrated that in the course of distillation the titanium oxoisopropoxy-2-ethylhexanoate is formed with elimination of ester ... 

The carbonylchloroiridium(III) porphyrins can be transformed into a variety of other carbonyl complexes by chloride exchange with acids or salts (path e). Concentrated sodium hydroxide in ethanol appears to destroy the carbonyl ligand in these compounds (path — d, a) in a manner similar to the alkoxide addition to RhCl(TPP) CO (path f) here, this should give a carboxylic acid RhCOOH(P) which is decarboxylated to a hydride RhH(P) according to the typical base reaction of metal carbonyls. The hydride may then be autoxidized to the hydroxide. 

The oxidation of alcohols to aldehydes, ketones or carboxylic acids is one of the commonest reactions in organic chemistry, and is frequently achieved by transition metal complexes or salts. However, in most cases the precise mechanisms are not known, and the intermediates not fully characterised. In general, metal complexes of the alcohols are formed as transient intermediates in these reactions, but we shall not deal with these extremely important reactions in any great detail. The precise mechanisms depend upon the accessibility of the various one- and two-electron reduction products of the particular metal ion which is involved in the reaction. However, we will outline a brief indication of the mechanism. The first step involves the formation of an alcohol complex of the metal ion (Fig. 9-14). This might or might not deprotonate to the alkoxide form, depending upon the pH conditions of the reaction, the pK of the alcohol and the polarising ability of the metal ion. 

Carboxylate complexes are often synthesized by refluxing the acid with the metal salts (such as carbonate, sulfate, oxide, etc.), or by reaction of the sodium or silver salt of the acid with the metal halide. Insertion of CO2 into a-bonded organotransition metal species has also been used to generate carboxylate complexes, as has exchange reactions with metal alkoxides (see Section 3.3). 

Computational studies suggest that the mechanism of the proline catalyzed aldol cyclization is best described by the nucleophilic addition of the neutral enamine to the carbonyl group together with hydrogen transfer from the proline carboxylic acid moiety to the developing alkoxide. A metal-free partial Zimmerman-Traxler-type transition state involving a chair-like arrangement of enamine and carbonyl atoms and the participation of only one proline molecule has been established [118,119]. On the basis of density functional theory (DFT) calculations Cordova and co-workers [120,121] have studied the primary amino acid intermolecular aldol reaction mechanism. They demonstrated that only one amino acid molecule is involved in the... 

In keeping with our general theme of presenting similarities between hetero-and homometal alkoxides, it may be pointed out that ester elimination was found to be a side reaction in the preparation of a metal carboxylate from the reaction between the alkoxide of a metal and a carboxylic acid leading to an oxo-car-boxylate and sometimes to an oxo-alkoxide at the intermediate stage(s) [cf. (6, 145)] ... 

The HTPs were then obtained by neutralization of the polymers in solution with highly reactive metal alkoxides or alkyl metals under strictly anhydrous conditions, following a procedure described in detail elsewhere (6,7). When the very rapid reaction is completed, the polymer is dried under vacuum to constant weight. Quantitative neutralization of the carboxylic acid groups can be achieved as evidenced by infrared spectroscopy. Once in the bulk state, all samples were kept under atmospheric conditions and protected from light. 

Most metal alkoxides are very reactive toward hydrolysis and condensation. They must be stabilized to avoid precipitation. The chemical control of these reactions is currently performed by adding complexing reagents that react with metal alkoxides at a molecular level, giving rise to new molecular precursors of different structure, reactivity, and functionality. Chemical modification is usually performed with hydroxylated nucleophilic ligands, such as carboxylic acids or P-diketones. In most cases complexation by XOH species can be described as a nucleophilic substimtion, as follows ... 

Bromine derivatives of thiophene are the most widely used for the preparation of isomeric thienothiophenes and related systems. A classical example is illustrated by the following transformation sequence formylation of 3,4-dibromothiophene (1) through lithium derivatives, repeated metallation and treatment with elemental sulfur and methyl bromoacetate. Ring closure of the second heterocycle occurs in the present of sodium alkoxide. Decarboxylation of the resulting 4-bromothieno[2,3-Z ]thiophene-2-carboxylic acid (2a) affords 3-bromothieno[2,3-Z)]thiophene (3a) (74IZV1570). The reaction with selenium instead of sulfur produced 4-bromosele-nolo[2,3-Z ]thiophene-2-carboxylic acid (2b) and 4-bromoselenolo[2,3-Z)]thiophene (3b). 

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