Alkali metals Group anions

The niobium-arseitic compounds described here, with novel anionic structures, clearly demonstrate the many possibilities for stractural motifs in this system. Similarly high potential for diverse structures and properties should be expected for the heavier pitictides when combined with other transition metals and the alkali-metal group. 

Surface Superbasic Sites of One-electron Donor Character. - The reaction of alkali metal with anionic vacancies on the oxide surfaces (equation 1) leads to the creation of colour centres of F type. The transfer of one electron from the alkali metal atom to an anionic vacancy is the reason for the formation of these defects. The largest quantities of this type of active centre are obtained by evaporation of the alkali metal onto an oxide surface calcined at about 1023 K, at which temperature the largest quantity of anionic vacancies is formed. Oxide surfaces calcined at such high temperatures contain only a small quantity of OH groups ca. 0.5 OH per 100 for MgO and 0.8 OH per 100 for AI2O3), so their role in the reaction is small and the action of alkali metal leads selectively to the creation of defects of the electron in anionic vacancy type. The evidence for such a reaction mechanism is the occurrence of specific colours in the oxide. Magnesium oxide after deposition by evaporation of sodium, potassium, or a caesium turns blue, alumina after sodium evaporation becomes a navy blue in colour, and silica after sodium evaporation becomes violet-brown in colour. ... 

Free ftom a transition metal, tiie boryl group is highly basic. The first fuUy diaracter-ized alkali metal boryl anion was reported in 2006 by Yamashita, Nozaki and co-workers. Previous studies on the generation of boryl anions have not been reproduced. Theoretical studies imply that much of the charge on a free boryl anion would actually reside on the substituents, and that the boron would bear positive charge. ... 

The solvent systems of this group include the solutions of mineral acids, carboxylic acids, and alkali salts prepared in a distilled or water-methanol mixture. These solvent systems being nontoxic and nonvolatile have been widely used in the separation of transition metals (57,64,67,73,79,81,82,86,92, 94,96,98,100,101,104-108,110,117,120,123), alkali metals (108), anions (136,142,146), metal-or-ganics (151,152,174,177,181,192), metal inorganic complexes (200) and rare earths (54,58,75,89,91, 109,127). 

The most common catalysts in order of decreasing reactivity are haUdes of aluminum, boron, zinc, and kon (76). Alkali metals and thek alcoholates, amines, nitriles, and tetraalkylureas have been used (77—80). The largest commercial processes use a resin—catalyst system (81). Trichlorosilane refluxes in a bed of anion-exchange resin containing tertiary amino or quaternary ammonium groups. Contact time can be used to control disproportionation to dichlorosilane, monochlorosilane, or silane. 

A number of compounds of the types RBiY2 or R2BiY, where Y is an anionic group other than halogen, have been prepared by the reaction of a dihalo- or halobismuthine with a lithium, sodium, potassium, ammonium, silver, or lead alkoxide (120,121), amide (122,123), a2ide (124,125), carboxylate (121,126), cyanide (125,127), dithiocarbamate (128,129), mercaptide (130,131), nitrate (108), phenoxide (120), selenocyanate (125), silanolate (132), thiocyanate (125,127), or xanthate (133). Dialkyl- and diaryUialobismuthines can also be readily converted to secondary bismuthides by treatment with an alkali metal (50,105,134) ... 

Several methods for the preparation of unsymmetrical sulfur diimides RN=S=NR have been developed. One approach involves the addition of a catalytic amount of an alkali metal to a mixture of two symmetrical sulfur diimides, RN=S=NR and RT8i=S=NR. A second method makes use of alkali-metal derivatives of [RNSN] anions.Eor example, derivatives in which one of the substituents is a fluoroheteroaryl group can be prepared by the reaction of the anionic nucleophile [RN=S=N] with pentafluoropyridine. Sulfur diimides of the type RN=S=NH (R = 2,4,6- Bu3C6H2S) have also been prepared. "... 

Arsenites of the alkali metals are very soluble in water, those of the alkaline earth metals less so, and those of the heavy metals are virtually insoluble. Many of the salts are obtained as meta-arsenites, e.g. NaAs02, which comprises polymeric chain anions formed by comer linkage of pyramidal ASO3 groups and held together by Na ions ... 

Alcohols undergo many reactions and can be converted into many other functional groups. They can be dehydrated to give alkenes by treatment with POCI3 and can be transformed into alkyl halides by treatment with PBr3 or SOCU- Furthermore, alcohols are weakly acidic (p/C, — 16-18) and react with strong bases and with alkali metals to form alkoxide anions, which are used frequently in organic synthesis. 

The reaction with 4-nitrophenol and pentafluorophenol in the presence of KF-18-crown-6 has been investigated. Pentafluorophenoxide anion was found to be a better leaving group [82JFC(20)439]. Alkali metal fluorides on graphite can act as catalysts for nucleophilic substitution of pentafluor-opyridine [90JFC(46)57]. 

The principal product of the reaction of the alkali metals with oxygen varies systematically down the group (Fig. 14.15). Ionic compounds formed from cations and anions of similar radius are commonly found to he more stable than those formed from ions with markedly different radii. Such is the case here. Lithium forms mainly the oxide, Li20. Sodium, which has a larger cation, forms predominantly the very pale yellow sodium peroxide, Na202. Potassium, with an even bigger cation, forms mainly the superoxide, K02, which contains the superoxide ion, O,. ... 

The alkali metals are usually found as singly charged cations. They react with water with increasing vigor down the group. Cations tend to form their most stable compounds with anions of similar size. 

This reaction is a principal method of forming IIIB-transition-metal cr bonds. The formation of thermodynamically favored alkali-metal halides or related salts and acids HX enhances the easy formation of those bonds. A second possible interaction between anionic metal bases and group-IIIB halides is a simple acid-base relationship without elimination of halide anions. However examples of this are rare, and they have been described often for group-IIIB compounds without halogen ligands ( 6.5.3.2). 

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