Ascorbic acid metal complexes

Masking by oxidation or reduction of a metal ion to a state which does not react with EDTA is occasionally of value. For example, Fe(III) (log K- y 24.23) in acidic media may be reduced to Fe(II) (log K-yyy = 14.33) by ascorbic acid in this state iron does not interfere in the titration of some trivalent and tetravalent ions in strong acidic medium (pH 0 to 2). Similarly, Hg(II) can be reduced to the metal. In favorable conditions, Cr(III) may be oxidized by alkaline peroxide to chromate which does not complex with EDTA. 

In acidic solution, the degradation results in the formation of furfural, furfuryl alcohol, 2-furoic acid, 3-hydroxyfurfural, furoin, 2-methyl-3,8-dihydroxychroman, ethylglyoxal, and several condensation products (36). Many metals, especially copper, cataly2e the oxidation of L-ascorbic acid. Oxalic acid and copper form a chelate complex which prevents the ascorbic acid-copper-complex formation and therefore oxalic acid inhibits effectively the oxidation of L-ascorbic acid. L-Ascorbic acid can also be stabilized with metaphosphoric acid, amino acids, 8-hydroxyquinoline, glycols, sugars, and trichloracetic acid (38). Another catalytic reaction which accounts for loss of L-ascorbic acid occurs with enzymes, eg, L-ascorbic acid oxidase, a copper protein-containing enzyme. 

Formazans and their metal complexes are used as textile dyes by direct application. The in situ reduction of tetrazolium salts has not been used to introduce the dyes to their substrates. Treatment with triaryl mono and bis tetrazolium salts followed by a reducing agent such as ascorbic acid or thioglycolic acid has been claimed as a method of introducing formazans as permanent hair dyes.641 There are some references to their use as therapeutic agents.642 544... 

Well-characterized transition metal complexes of vitamin C (ascorbic acid) are rare, and a select number of these exhibit anticancer properties. Hollis et al. have described the first examples to be fully characterized by X-ray crystallography.316 Treatment of [Pt(H20)2L2]2+ (L = NH3, MeNH2 L2 = en, 1,2-chxn) with ascorbic acid gives either the mono- or bisascorbate species of the type cis-[PtL2(C2,Os-ascorbate)] (e.g., (125)) or m-[PtL2(C2-ascorbate)(03-ascorbate)], respectively. Interestingly, in both types of complexes, platinum(II) forms a bond with the C-2 atom of ascorbic... 

The same model was applied to the oxidation of the H2A form of ascorbic acid. In this case iron(III) was found to be a somewhat more active catalyst than copper(II). The difference could be explained by assuming that Fe(III) forms a more stable complex with H2A than does Cu(II) because of the higher charge of the metal ion. 

The formation of the [M(HA)](" 1>+ complex was confirmed in independent pH-metric experiments in the case of copper(II). These studies also provided evidence that ascorbic acid is coordinated to the metal center in its monoprotonated form. Because of relatively fast redox reactions between iron(III) and ascorbic acid, similar studies to confirm the formation of [Fe(HA)]2+ were not feasible. However, indirect kinetic evidence also supported the formation of the [M(HA)](" 1>+ complex in both systems (6). 

Iron(III)-catalyzed autoxidation of ascorbic acid has received considerably less attention than the comparable reactions with copper species. Anaerobic studies confirmed that Fe(III) can easily oxidize ascorbic acid to dehydroascorbic acid. Xu and Jordan reported two-stage kinetics for this system in the presence of an excess of the metal ion, and suggested the fast formation of iron(III) ascorbate complexes which undergo reversible electron transfer steps (21). However, Bansch and coworkers did not find spectral evidence for the formation of ascorbate complexes in excess ascorbic acid (22). On the basis of a combined pH, temperature and pressure dependence study these authors confirmed that the oxidation by Fe(H20)g+ proceeds via an outer-sphere mechanism, while the reaction with Fe(H20)50H2+ is substitution-controlled and follows an inner-sphere electron transfer path. To some extent, these results may contradict with the model proposed by Taqui Khan and Martell (6), because the oxidation by the metal ion may take place before the ternary oxygen complex is actually formed in Eq. (17). 

It is not clear either how the Ru center can accommodate four ligands simultaneously. The crowded coordination sphere around the metal center in the Ru(EDTA)-ascorbate complex is expected to hinder the coordination of other ligands as was proposed earlier (24,25). The contradiction between the two sets of results reported in Refs. (24,25) and (148) is obvious. While the Ru(EDTA)(H2A)(02) complex was not considered in the kinetic model proposed for the oxidation of ascorbic acid,... 

An extractive spectrophotometric procedure based on the complexation of reduced Iron(II) with 5-Chloro-7-iodo-8-hydroxyquinoline (CIHQ) for the estimation of micro amounts of vitamin C. The resulting brown colored complex was extracted into chloroform to give a reddish brown extract which shows an absorption band at 485 nm. This chelate was formed immediately and the apparent molar absorptivity and Sandell s sensitivity for vitamin C was found to be 8.5 x 105 dm3 mol"1 cm 1 and 2.072xl0 4g cm 2. Linear relationship between absorbance and concentration of ascorbic acid is observed up to 0.8 pg ml"1. Interference studies of different substances including sugars, vitamins and amino acids, metal ions and organic acids were carried out. The utility of the method was tested by analysing some of the marketed products of vitamin C... 

Argenlalion chromalography, 261 Aromatic acids in human urine, 285 Aromatic hydrocarbons, 69 Arylhydroxylamines, 298 Ascorbic acid, 296 Aspirin, 282 Asymmetric diens, 290 Asymmetrical peaks, 58, 82, 160 AIT, stability constants of metal complexes. 278 Atrazine, 292 Atropine, 297 Axial diffusion mobile phase. 8 stationary phase, 8,9 Aza-arenes, 293 Azoxybenzenes, 298... 

Berkessel and Sklorz screened a variety of potential co-ligands for the Mn-tmtacn/H202 catalyzed epoxidation reaction and found that ascorbic acid was the most efficient one. With this activator the authors could oxidize the terminal olefins 1-octene and methyl acrylate with full conversion and yields of 83% and 97%, respectively, employing less than 0.1% of the metal complex (Scheme 86). Furthermore, with E- and Z-l-deuterio-1-octene as substrates, it was shown that the oxygen transfer proceeded stereoselectively with almost complete retention of configuration (94 2%). Besides the epoxidation, also the oxidation of alcohols to carbonyl compounds could be catalyzed by this catalytic system (see also Section in.C). 

Metal complexes catalyze oxidation of compounds having mobile hydrogens, such as ascorbic acid, hydroquinone, phenols, and amines, in the presence of molecular oxygen [Eq. (16)]. In this reaction, a substrate coordinates to the metal catalyst,... 

The electrostatic effect of the poly(4-vinylpyridine)-Cu(II) catalyst was also reported by Dadze et al. 115). Oxidation of ascorbic acid, salicylic acid, and tri-t-butylphenol was accelerated and that of p-phenylenediamine retarded by the poly(4-vinylpyridine) ligand at lower pH. As described in Section IIIA, a polymer-metal complex behaves as a polycation in aqueous solution, and the reaction is sensitive to the charge of low-molecular-weight species. The electrostatic effect due to the polycationic domain of a polymermetal catalyst is also predominant in the oxidation of charged substrates. 

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