Metal carboxylic acids

Entries where the oxidation state of a metal has been specified occur after all the entries for the unspecified oxidation state, and the same or similar entries may occur under both types of heading. Thus cyanide appears under Chromium complexes, Chromium(O) complexes, Chromium(I) complexes, etc. More specific entries, such as Chromium, hexacyano-, may also occur. Similar ligands may also occur in different entries. Thus a carboxylic acid-metal complex may occur under Carboxylic acid complexes, under entries for specific carboxylic acids, and under the specific metal. Coordination complexes may also be listed in the Cumulative Formula Index. 

Metal carbonyls proved to be superior to earlier catalytically active systems, where in particular strong acids were used [4], because the conditions, namely pressure and temperature, that had to be applied led to skeletal isomerization of the substrates and resulted predominantly in the formation of branched isomers of carboxylic acids. Metal carbonyls were of great advantage over the older catalysts in this respect. Despite the fact that it was possible to optimize the catalyst metal, the ligands, and the promoters for nearly every carbonylation reaction, enabling the reactions to take place under milder conditions than had been previously used, these processes could only be realized industrially after the development of appropriate reactor materials because of the corrosive properties of the reaction media and products. 

IV. Reactions of Metalated Carboxylic Acids - Metalated carboxylic acids react with most electrophiles It the dianlon is associated with alkali metal cations. However, Cu(i) dianions22 react readily only with activated allylic or benzylic halides. 

Ions that are most commonly determined in food samples are inorganic anions, carboxylic acids, metal ions, and organic cations. Some anion-exchange stationary phases do not always allow a baseline-resolved separation of all inorganic and organic ions under isocratic conditions. 

A -Thiazoline-4-carboxylic acids, metalation 26, 644s32 A -Thiazoline ring opening... 

Aronoff Y G, Chen B, Lu G, Seto C, Schwartz J and Bernasek S L 1997 Stabilization of self-assembled monolayers of carboxylic acids on native oxides of metals J. Am. Chem. Soc. 119 259-62... 

Note. Useful information can often be obtained by adding (i) dilute H,SO or (ii) dilute NaOH solution to an aqueous solution of the substance under investigation. A precipitate with (i) usually indicates an aromatic carboxylic acid from a metallic or from an ammonium salt. A precipitate or oil with (ii) usually indicates an aromatic amine from an amine salt. 

The silver salts of most carboxylic acids are only sparingly soluble in cold water, and hence are readily prepared. Moreover they very rarely contain water of crystallisation, and therefore when dried can be analysed without further treatment. The analysis itself is simple, rapid and accurate, because gentle ignition of a weighed quantity of the silver salt in a crucible drives off the organic matter, leaving a residue of pure metallic silver. 

Perhaps the most extensively studied catalytic reaction in acpreous solutions is the metal-ion catalysed hydrolysis of carboxylate esters, phosphate esters , phosphate diesters, amides and nittiles". Inspired by hydrolytic metalloenzymes, a multitude of different metal-ion complexes have been prepared and analysed with respect to their hydrolytic activity. Unfortunately, the exact mechanism by which these complexes operate is not completely clarified. The most important role of the catalyst is coordination of a hydroxide ion that is acting as a nucleophile. The extent of activation of tire substrate througji coordination to the Lewis-acidic metal centre is still unclear and probably varies from one substrate to another. For monodentate substrates this interaction is not very efficient. Only a few quantitative studies have been published. Chan et al. reported an equilibrium constant for coordination of the amide carbonyl group of... 

Inspired by the many hydrolytically-active metallo enzymes encountered in nature, extensive studies have been performed on so-called metallo micelles. These investigations usually focus on mixed micelles of a common surfactant together with a special chelating surfactant that exhibits a high affinity for transition-metal ions. These aggregates can have remarkable catalytic effects on the hydrolysis of activated carboxylic acid esters, phosphate esters and amides. In these reactions the exact role of the metal ion is not clear and may vary from one system to another. However, there are strong indications that the major function of the metal ion is the coordination of hydroxide anion in the Stem region of the micelle where it is in the proximity of the micelle-bound substrate. The first report of catalysis of a hydrolysis reaction by me tall omi cell es stems from 1978. In the years that... 

The less hindered f/ans-olefins may be obtained by reduction with lithium or sodium metal in liquid ammonia or amine solvents (Birch reduction). This reagent, however, attacks most polar functional groups (except for carboxylic acids R.E.A. Dear, 1963 J. Fried, 1968), and their protection is necessary (see section 2.6). 

Carboxylic acids react with butadiene as alkali metal carboxylates. A mixture of isomeric 1- and 3-acetoxyoctadienes (39 and 40) is formed by the reaction of acetic acid[13]. The reaction is very slow in acetic acid alone. It is accelerated by forming acetate by the addition of a base[40]. Addition of an equal amount of triethylamine achieved complete conversion at 80 C after 2 h. AcONa or AcOK also can be used as a base. Trimethylolpropane phosphite (TMPP) completely eliminates the formation of 1,3,7-octatriene, and the acetoxyocta-dienes 39 and 40 are obtained in 81% and 9% yields by using N.N.N M -tetramethyl-l,3-diaminobutane at 50 in a 2 h reaction. These two isomers undergo Pd-catalyzed allylic rearrangement with each other. 

Metal carboxylates are ionic and when the molecular weight isn t too high the sodium and potassium salts of carboxylic acids are soluble m water Carboxylic acids therefore may be extracted from ether solutions into aqueous sodium or potassium hydroxide... 

FIGURE 19 6 Space filling model of a micelle formed by association of car boxylate ions derived from a long chain carboxylic acid The hydrocarbon chains tend to be on the inside and the carboxylate ions on the surface where they are in contact with water mole cules and metal cations... 

Polarography is used extensively for the analysis of metal ions and inorganic anions, such as lOg and NOg. Organic compounds containing easily reducible or oxidizable functional groups also can be studied polarographically. Functional groups that have been used include carbonyls, carboxylic acids, and carbon-carbon double bonds. 

Salt Formation. Salt-forming reactions of adipic acid are those typical of carboxylic acids. Alkali metal salts and ammonium salts are water soluble alkaline earth metal salts have limited solubiUty (see Table 5). Salt formation with amines and diamines is discussed in the next section. 

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