Alkali metal complexes acid salts

Bis(dialkyldithiophosphinato)nickel(II) complexes were prepared by the direct synthesis of an alkali metal or ammonium salt of the dithiophosphinic acid and a nickel salt in aqueous solution.2039,2061"2063 Ni(S2AsR2)2 and Ni(Se2PR2)2 complexes were prepared in a similar way.2064"2066 All of these complexes are square planar like their dithiophosphate analogues. X-Ray crystal structures of the complexes Ni(S2PR2)2, with R = Me,2067 Et, Ph,1983 R2 = Me/ Et 2°w r2 = Me/2-thienyl,2069 and Ni(Se2PPh2)21984 have been reported (Table 90). 

Adenosine triphosphate alkali metal complexes, 34 vanadyl complexes, 568 Alane, 123 amine adducts, 107 phosphine adducts, 111 Alane, alkoxy-, 124 Alane, amino-, 109 Alane, imino-, 109 Alkali metal complexes, 1-70 acid anions, 30 acid salts, 30 bipyridyl, 13 crown ethers cavity size, 38 cryptates... 

Polypyridine Torand 1. Complexes of alkali metal triflates and picrates have been prepared from the monotriflate salt of torand 1, which is isolated directly from the macrocyclization reaction mixture. As shown in Figure 3, neutralization of the triflate salt with alkali metal hydroxides or carbonates gives the alkali metal complexes. With triflate or picrate counterions, torand complexes and salts partition selectively into chlorofonn rather than water. Thus 1 can be shuttled back and forth between the triflate salt and various complexes simply by washing the chloroform solution with aqueous acid or base. The free ligand is prepared by reaction of the triflate salt with tetra-n-butylammonium hydroxide in butanol/acetonitrile. Combustion microanalysis showed that the Li, Na, K, Rb and Cs complexes all have 1 1 host/guest stiochiome-try, despite the cavity/ion size mismatch at both ends of the series. The X-ray crystal... 

In this chapter, we reviewed recent developments regarding lithium, sodium, and potassium salt based-catalysis, with a particular focus on asymmetric catalysts. While these alkali-metal salts have traditionally been used as simple bases, recent advances based on chiral multifunctional acid-base combination chemistry, using chiral crown-alkali-metal complexes, chiral lanthanoid/alkali-metal complexes, chiral alkali-metal alkoxides, and chiral alkali-metal phosphates, have also been outstanding. These synergic acid-base catalyst systems should enable more efficient and/or new transformations that have not been possible thus far using conventional catalysts that only rely on Lewis acidity or Bronsted/Lewis basicity. 

Compounds of Tl have many similarities to those of the alkali metals TIOH is very soluble and is a strong base TI2CO3 is also soluble and resembles the corresponding Na and K compounds Tl forms colourless, well-crystallized salts of many oxoacids, and these tend to be anhydrous like those of the similarly sized Rb and Cs Tl salts of weak acids have a basic reaction in aqueous solution as a result of hydrolysis Tl forms polysulfldes (e.g. TI2S3) and polyiodides, etc. In other respects Tl resembles the more highly polarizing ion Ag+, e.g. in the colour and insolubility of its chromate, sulfide, arsenate and halides (except F), though it does not form ammine complexes in aqueous solution and its azide is not explosive. 

Block copolymers of (R,S)-(3-butyrolactone and eCL have been synthesized by combining the anionic ROP of the first monomer with the coordinative ROP of the second one (Scheme 15) [71]. The first step consisted of the synthesis of hydroxy-terminated atactic P(3BL by anionic polymerization initiated by the alkali-metal salt of a hydroxycarboxylic acid complexed with a crown ether. The hydroxyl end group of P(3BL could then be reacted with AlEt3 to form a macroinitiator for the eCL ROP. 

Other complexes described by the early workers include salicyl-aldehyde, o-nitrophenols, and acetylacetone as possible neutral ligands, HL, so that compounds of composition ML, HL or ML, HL were obtained. These were referred to as acid salts and illustrate the difficulty of deciding on a criterion for complex formation. Sfieakman (5)has reviewed the crystal structures of many acid salts of alkali metals in an investi-... 

The latter also forms complex salts of alkali metals M2PbCl4 and MPb2Cl5. Lead dichloride is hydrolyzed by steam to a basic chloride Pb(OH)Cl and hydrochloric acid ... 

Alkali metal salts of such tetracyanonickelate(II) anion may be crystallized from such solutions as hydrates, K2 [Ni(CN)4 3H2O upon evaporation of the solution. In strong cyanide solution, a pentacyano complex anion, red penta-cyanonickelate(ll), [Ni(CN)5] forms. Strong acids decompose cyanonickelate salts, precipitating nickel cyanide. 

These titrations arc used in the estimation of metal salts. Ethylenediamine tetracetic acid (EDTA) shown in Figure 3.10 is the usual titrant used. It forms stable 1 1 complexes with all metals except alkali metals such as sodium and potassium. The alkaline earth metals such as calcium and magnesium form complexes which are unstable at low pH values and are titrated in ammonium chloride buffer at pH 10. The general equation for the titration is ... 

CO2 molecule, or Mg + and CO2 play the role of oxide acceptor to form water, carbonate, and MgC03, respectively [38]. The reactions of the iron carboxylate with these Lewis acids are thought to be fast and not rate determining. For the cobalt and nickel macrocyclic catalysts, CO2 is the ultimate oxide acceptor with formation of bicarbonate salts in addition to CO, but it is not clear what the precise pathway is for decomposition of the carboxylate to CO [33]. The influence of alkali metal ions on CO2 binding for these complexes was discussed earlier [15]. It appears the interactions between bound CO2 and these ions are fast and reversible, and one would presume that reactions between protons and bound CO2 are rapid as well. 

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