Carboxylic acids metal complexes

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. 

The methylene group of a-amino acid metal complexes such as the copper(II) glycinato complex is activated to some extent by the polarizing influence of the metal.46,47 Consequently, carban-ion-type reactions can be carried out at this position, while the amino and carboxyl groups are protected by coordination. These reactions cannot be performed on either the free ligand or the conjugate base. 

Although the calixarene carboxylic acids form complexes with some of the alkali metal cations, the fact that they have an even greater capacity for alkaline earth cations was first realized in the mid 1980s and subsequently studied in some detail. As a consequence of their greater charge the alkaline... 

Carboxylates (like amino groups) can also bind to Lewis acidic metal complexes, such as Zn-porphyrinates. In receptor 30. derived from an A -methyl porphyrin, the methyl group blocks an approach from the lower face. A carboxylate counterion must, therefore, coordinate to the top face, in the chiral environment created by the strap. When 30 (X = OAc) was dissolved in CHCI3 ani shaken with aqueous IV-acyl amino acids, many of the carbox-ylates were extracted with >80% e.e. ... 

Epoxidized PBDs react with carbon dioxide to form cyclic carbonates. The reaction is catalyzed by Lewis acidic metal-complexes, especially effectively by tetrabutyl ammonium cations and lithium salts to give carboxylated products at ambient pressure in a carbon dioxide atmosphere. The resulting material showed interactions with lithium ions, making it suitable for preparing lithium-conducting membranes (Scheme 14) [178]. 

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... 

Calcon carboxylic acid [3-hydroxy-4-(2-hydroxy-4-sulfo-l-napbtbylazo)napbtbalene-2-carboxylic acid] [3737-95-9] M 428.4, m 300°, X,max 560nm, pKj 1.2, pK2 3.8, PK3 9.26, PK4 13.14. Purified through its p-toluidinium salt. The dye was dissolved in warm 20% aq MeOH and treated with p-toluidine to ppte the salt after cooling. Finally recrystd from hot water. [Itoh and Ueno Analyst (London) 95 583 1970.] Patton and Reeder (Anal Chem 28 1026 1956) indicator and complexes with Ca in presence of Mg and other metal ions. 

When a Br nsted base functions catalytically by sharing an electron pair with a proton, it is acting as a general base catalyst, but when it shares the electron with an atom other than the proton it is (by definition) acting as a nucleophile. This other atom (electrophilic site) is usually carbon, but in organic chemistry it might also be, for example, phosphorus or silicon, whereas in inorganic chemistry it could be the central metal ion in a coordination complex. Here we consider nucleophilic reactions at unsaturated carbon, primarily at carbonyl carbon. Nucleophilic reactions of carboxylic acid derivatives have been well studied. These acyl transfer reactions can be represented by... 

The second type of trinuclear compounds containing (M302(02CR)(,(H20)3] and obtained by the reaction of M(CO)6 (M = Mo, W) with carboxylic acids, features a similar triangle of M-M bonded metal atoms but this time capped on both sides by hj-O atoms (Fig, 23.8d). Complexes m which either one or both of these capping atoms arc replaced by /iy-CR, alkylidene. 

Guo et al. [70,71,73] recently attempted to hydrogenate NBR in emulsion form using Ru-PCy complexes. However, successful hydrogenation can only be obtained when the emulsion is dissolved in a ketone solvent (2-butanone). A variety of Ru-phosphine complexes have been studied. Crosslinking of the polymer could not be avoided during the reaction. The use of carboxylic acids or first row transition metal salts as additives minimized the gel formation. The reactions under these conditions require a very high catalyst concentration for a desirable rate of hydrogenation. 

The observation that addition of imidazoles and carboxylic acids significantly improved the epoxidation reaction resulted in the development of Mn-porphyrin complexes containing these groups covalently linked to the porphyrin platform as attached pendant arms (11) [63]. When these catalysts were employed in the epoxidation of simple olefins with hydrogen peroxide, enhanced oxidation rates were obtained in combination with perfect product selectivity (Table 6.6, Entry 3). In contrast with epoxidations catalyzed by other metals, the Mn-porphyrin system yields products with scrambled stereochemistry the epoxidation of cis-stilbene with Mn(TPP)Cl (TPP = tetraphenylporphyrin) and iodosylbenzene, for example, generated cis- and trans-stilbene oxide in a ratio of 35 65. The low stereospecificity was improved by use of heterocyclic additives such as pyridines or imidazoles. The epoxidation system, with hydrogen peroxide as terminal oxidant, was reported to be stereospecific for ris-olefins, whereas trans-olefins are poor substrates with these catalysts. 

Pinacolone, o-(diphenylphosphino)benzoyl-coordination chemistry, 2, 401 Ping-pong reactions copper(II) complexes, 5, 717 Piperidine, /V-hydroxy-metal complexes, 2, 797 P a values azole ligands, 2, 77 Plant roots amino acids, 2, 962 carboxylic adds, 2,962 Plants... 

Quinoline, 8-mercapto-2-methyl-metal complexes, 2, 800 Quinoline, 2-methyl-8-(methylthio)-metal complexes, 2,801 Quinoline, 8-methylthio-metal complexes, 2, 801 Quinoline-2-carboxylic-acid, 8-hydroxy-methyl ester... 

Heimann and Vogtle [38] synthesized triesters of glycerol with different ether carboxylic acids with a short alkyl chain. They have found that these hydrophilic lipids, in contrast with the fatty acid glycerol triesters, give complex-ation with alkali and alkali earth metal cations in an analogy of crown ethers. 

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