Hydroxide anion complexes

After preparing a homogeneous solution of the precursors, powder precipitation is accompHshed through the addition of at least one complexing ion. For PLZT, frequently OH in the form of ammonium hydroxide is added as the complexing anion, which results in the formation of an amorphous, insoluble PLZT-hydroxide. Other complexing species that are commonly used are carbonate and oxalate anions. CO2 gas is used to form carbonates. Irrespective of the complexing anion, the precipitated powders are eventually converted to the desired crystalline oxide phase by low temperature heat treatment. 

As shown in this table, the metal catalysts used in the literature are mostly complexes of Ni or Cu and less often Co or Pd. For soft nucleophiles, on the left of the table, the efficiency of the nickel catalysts was already reported. Here, are presented the investigations concerning the arylation of hard nucleophiles such as amines, alcohols or hydroxide anion, using Ni, Pd and Cu catalysts. 

Anionic complexes can easily be prepared by the sulfonation of the aromatic rings in the complexes. Sulfonated cobalt phthalocyanine intercalated in a layered double hydroxide host was a stable catalyst for the oxidation of thiols162,163 and phenol derivatives.164 It was concluded that the complex has been intercalated with the plane of the phthalocyanine ring perpendicular to the sheet of the host (edge-on orientation) (Fig. 7.2). 

A mechanism similar to Scheme 10 was proposed, involving CO addition, followed by H20 addition (in lieu of hydroxide anion) to form a metallocarboxylic acid complex. Then, decomposition to C02 and a metal hydride was proposed, followed by hydride elimination. Table 15 provides data from reaction testing in the temperature range 140 to 180 °C. In later testing, they compared Rh and Ir complexes for the reduction of benzalacetone under water-gas shift conditions. 

Concerning the synthesis of graft copolymers, Jedlinski et al. have prepared poly(MMA-g-(3BL) copolymers via anionic grafting of 3BL from a modified PMMA backbone [85]. PMMA chains were partially saponified by potassium hydroxide and complexed by 18C6 crown ether so as to act as multifunctional mac-... 

Ort/io-phenylene diboranes constitute another important class of polydentate Lewis acids which have been considered for the complexation of anions.In this context, most efforts have centered on the study of the ligative behavior of 1,2-bis(bis(pentaliuorophenyl)boryl)tetraliuorobenzene (17). Similar to 22, compound 17 forms chelate fluoride ([17- r2-F] ) and hydroxide ([17- r2-OH] ) complexes when treated with KF/18-C-6 and KOH/18-C-6, respectively (18-C-6 = 18-crown-6) (Scheme 35). The crystal structure of these anionic complexes has not been... 

Cadmium hydroxide is more basic than zinc hydroxide. It forms anionic complex Cd(OH)42 when treated with concentrated caustic soda solution. It forms complexes with cyanide, thiocyanate and ammonium ions when added to the solutions of these ions. 

The aqua complexes of Ee + and Ee +, which are present in acid solutions, can hydrolyze to EeOH+, Ee(OH) +, Ee(OH)2", and other ions at higher pH values, and the respective hydroxides precipitate. Weak anion complexes such as EeS04, EeS04+, or EeCh+ can also be formed. 

The initial nucleation stage of the complex-decomposition mechanism is probably similar to the simple free-anion mechanism. Either ionic or molecular metal species (ion-by-ion) or Cd(OH)2 (cluster) adsorbs on the substrate. However, instead of conversion of the hydroxide to sulphide by topotactic reaction with sulphide ions, the chalcogenide precursor (in almost all studies of this mechanism, that is thiourea) adsorbs on the Cd(OH)2 surface to form a hydroxide-thiourea complex, which then decomposes to CdS. 

Studies of the solubility of polonium(IV) in formic, acetic, oxalic and tartaric acids have provided evidence of complex formation,48 with the acetato complex emerging as more stable than the hexachloro anion. Other studies of the solubility of polonium(IV) hydroxide in carbonate49 and nitrate50 solution, together with investigations51 of the ion exchange behaviour of polonium(IV) at high nitrate ion concentration, have been discussed in terms of the formation of anionic complex species. 

The performance of calixarenes as cation carriers through H20-organic solvent H20 liquid membranes has also been studied.137 In basic metal hydroxide solutions, the monodeprotonated phenolate anions complex and transport the cations, while [18]crown-6 does not, under the same conditions. Low water solubility, neutral complex formation and potential coupling of cation transport to reverse proton flux have been cited as desirable transport features inherent in these molecules.137... 

Anion-exchange resins are eluted either by reversal of the equilibria shown in equations (94) to (96) or, in some cases, by chemical destruction of the anionic complex ML/-. The elution of strong-base resins requires a large excess of the co-ion, X-, whereas the elution of weak-base resins can be achieved most effectively by treatment of the resin with a stoichiometric amount of hydroxide ions, which restores the resin to the free-base form ... 

The ester-substituted complex (34) has been used in synthesis of (+)- and (-)-shikimic acid, an important intermediate in the biosynthesis of aromatic compounds, as well as stereospecifically deuterium labeled shikimic acid.60 Addition of hydroxide anion to (+)-(34) gives the diene complex (+)-(182),... 

Lopez Garcia et al. [2] have described a rapid and sensitive spectrophotometric method for the determination of boron complex anions in plant extracts and waters which is based on the formation of a blue complex at pH 1 - 2 between the anionic complex of boric acid with 2,6-dihydroxybenzoic acid and crystal violet. The colour is stabilised with polyvinyl alcohol. At 600 nm the calibration graph is linear in the range 0.3-4.5 xg boron per 25 ml of final solution, with a relative standard deviation of 2.6% for xg/l of boron. In this procedure to determine borate in plant tissues, the dried tissue is treated with calcium hydroxide, then ashed at 400 °C. The ash is digested with 1N sulfuric acid and heated to 80 °C, neutralized with cadmium hydroxide and then treated with acidic 2,6-dihydroxybenzoic acid and crystal violet, and the colour evaluated spectrophotometrically at 600 nm. Most of the ions present in natural waters or plant extracts do not interfere in the determination of boron complex anions by this procedure. Recoveries of boron from water samples and plant extracts were in the range of 97 -102%. 

Tests on synthesized biomimics indicated their high catalase activity (specifically for these applied on A1202) in H202 dissociation. It is the author s opinion that these studies gave essentially important results for explaining the Chance complex formation. It consists of bonding of Fe3+ ion in the sixth coordinate position in the biomimic to hydroxide anion. In this very form it manifests catalase activity. 

In 1998, Krebs and co-authors reported the crystal structures of the catechol oxidase isolated from sweet potatoes (Ipomoea batatas) in three catalytic states the native met (CunCun) state (Figure 5.2a), the reduced deoxy (Cu Cu1) form, and the complex with the inhibitor phenylthiourea (Figure 5.2b) [19]. Typically for the type 3 active site, each copper ion is coordinated by three histidine residues from the protein backbone. In the native met state, the two copper ions are 2.9 A apart and, in addition to six histidine residues, a bridging solvent molecule, most likely a hydroxide anion, has been refined in close proximity to the two metal centers... 

Because of the presence of nitrogen in the aromatic ring, electrons in pyridine are distributed in such a way that their density is higher in positions 3 and 5 (the P-positions). In these positions, electrophilic substitutions such as halogenation, nitration, and sulfonation take place. On the contrary, positions 2, 4, and 6 (a- and y-positions, respectively) have lower electron density and are therefore centers for nucleophilic displacements such as hydrolysis or Chichibabin reaction. In the case of 3,5-dichlorotrifluoropyridine, hydroxide anion of potassium hydroxide attacks the a- and y-positions because, in addition to the effect of the pyridine nitrogen, fluorine atoms in these position facilitate nucleophilic reaction by decreasing the electron density at the carbon atoms to which they are bonded. In a rate-determining step, hydroxyl becomes attached to the carbon atoms linked to fluorine and converts the aromatic compound into a nonaromatic Meisenheimer complex (see Surprise 67). To restore the aromaticity, fluoride ion is ejected in a fast step, and hydroxy pyridines I and J are obtained as the products [58],... 

Phenomena such as chemical and biological transformations, metal mobility, bioavailability, bioaccumulation, toxicity, and persistence in the environment frequently depend on the chemical form or speciation of a given ion, especially the metallic ions. For example, there is normally a great difference between the sorption behavior of a free metal cation and that of its anionic complexes onto mineral oxides and hydroxides. 

As in the phase-transfer procedures for preparation of > -allyl complexes of Mo, Mn, etc., the reaction proceeds through initial attack of a hydroxide anion on a coordinated CO. Subsequent decarboxylation results in formation of a tetracarbonyl anion, [Co(CO)4] , which is the reactive species ". ... 

Sorption in most soils attains a maximum when the neutral hydroxy complex of uranium is at a maximum. However, at pH 6 and above, and in the presence of high carbonate or hydroxide concentrations, uranium may form anionic complexes such as [U02(0H)4]. The mobility of anionic uranium complexes in soil is dependent upon the nature of the soil. For example, the decrease in sorption in soil with little anion-exchange capacity may result in increased mobility however, increased sorption in soil with high anion-exchange may result in decreased mobility (Allard et al. 1982 Ames et al. 1982 Brookins et al. 1993 Ho and Doern 1985 Hsi and Langmuir 1985 Tichnor 1994). 

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