Reactions of metal salts

Volume 6 Volume 7 Reactions of Non-metallic Inorganic Compounds Reactions of Metallic Salts and Complexes, and Organometallic Compounds Section 4. ORGANIC REACTIONS (6 volumes)... 

Reactions of Metallic Salts and Complexes, and Organometallic Compounds... 

In volume 7 reactions of metallic salts, complexes and organometallic compounds are covered. Isomerisation and group transfer reactions of inert metal complexes and certain organometallics (not involving a change in oxidation state) are considered first, followed by oxidation-reduction processes (a) between different valency states of the same metallic element (b) between salts of different... 

Allenyl cations have been generated by solvolysis of allenic derivatives, by photolysis of allenyl halides and by reaction of metal salts with allenyl and propargyl halides. This review will delineate these reactions. The related butatrienyl cations are not many and they will be only briefly described. 

TiTany commercial uses of carbohydrates depend upon reversible inter- actions of the hydroxyl groups with ions to form complexes. The processes are intricate, and analyses of the equilibria involved have been difficult or impossible (I). For example, the nature of the complexes involving polysaccharides and polyanions, such as borate, can only be hypothesized (2). Similarly the gelling of pectates with Ca(II) (3), the reactions of heptono-y-lactones with Fe(III), or the nature of Fe(III)-dextran complexes in intramuscular injectable solutions are awaiting proper description. Although the systems involving monomeric components are more amenable to study, as for the reactions of metal salts or hydroxides with monosaccharides or their simple derivatives (4,5, 6, 7)... 

The reactions of metal salts with organic azides RN3 appear to be strongly dependent on the nature of R which can be accounted for by the view that both routes a and b in Scheme 7 may be... 

Reactions of Metal Salts with Amine Salts... 

Although inefficient and mechanistically mysterious, these transformations highlight the reactivity inherent in the C—H bond of unsubstituted dithiolenes, a fertile area for further research (see Eq. 20). Benzenehexathiolate complexes can also of course be prepared by reactions of metal salts with C6(SH)6 or its salts (see Section II.A) (144, 146). 

A number of reactions of metal salts can be rationalized in terms of the formation of a carbanion adjacent to the carboxylate. Dibasic metals such as calcium bring two carboxylate units close to each other so that the carbanion formed adjacent to one carboxylate may attack the carbonyl of the other. Thus pyrolysis of calcium acetate affords propanone (acetone) (Scheme 3.62). A similar reaction is found in the pyrolytic cyclization of some dicarboxylic acid anhydrides. Heating Cg and dicarboxylic acids gives cyclopentanones and cyclohexanones... 

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