Sodium compounds, organo reactions with

Alkali metals can be intercalated into MPS3 either by chemical or electrochemical techniques. Chemical intercalation takes place when the host is reacted with an organo-alkali metal compound such as n-butyllithium or sodium napthalide. The reaction with n-butyllithium can be represented as ... 

Also other reaction types have been dealt with in CHEC(1984) and CHEC-II(19%) like reduction to alcohols (e.g., sodium borohydride), Wolff Kishner reduction, nucleophilic addition via reaction with Grignard reagents or organo-lithium compounds, and formation of imine type functional groups (e.g., hydrazones). New examples are the reaction of... 

For the explanation of this reaction it is usually assumed that sodium reacts with the monohalogen, forming an unstable compound in which the sodium is directly attached to the carbon, and that the organo-metallic compound then reacts with a second molecule of the halide to form the hydrocarbon ... 

This theory of the mechanism of sodium reactions represents an extension of Morton s views on the directive effect of the cation in the reactions of organo-sodium compounds (22,23). He considers the initiation of organosodium reactions to involve coordination of the sodium with a center of high electron density the similarity of this concept to our theory of metallic sodium reactions is obvious. 

The acetylide anions discussed in Chapter 11 are another example of organometallic compounds. These reagents are prepared by an add-base reaction of an alkyne with a base such as NaNH2 or NaH. We can think of these componnds as oi anosodium reagents. Because sodium is even more electropositive (less electronegative) than lithinm, the C-Na bond of these organo-sodium compounds is best described as ionic, rather than polar covalent. 

Sodium has been widely used in the synthesis of various organo-metals and organo-metalloids, by causing the halides of the elements to react with organic halogen compounds. The following are examples of this type of reaction ... 

The reaction of a Co(I) nucleophile with an appropriate alkyl donor is used most frequently for the formation of a Co-C bond, which also can be formed readily by addition of a Co(I) complex to an acetylenic compound or an electron-deficient olefin (5). The nu-cleophilicity of Co(I) in Co(I)(BDHC) is expected to be similar to that in the corrinoid complex, as indicated by their redox potentials. The formation of Co-C a-bond is the attractive criterion for vitamin Bi2 models. Sodium hydroborate (NaBH4) was used for the reduction of Co(III)(CN)2(BDHC) in tetrahydrofuran-water (1 1 or 2 1 v/v). The univalent cobalt complex thus obtained, Co(I)(BDHC), was converted readily to an organometallic derivative in which the axial position of cobalt was alkylated on treatment with an alkyl iodide or bromide. As expected for organo-cobalt derivatives, the resulting alkylated complexes were photolabile (17). 

Triphasic systems involving clays pillared with surfactants as catalysts offer versatile routes to a range of useful benzylic compounds.40 By using the organo-clay assemblies with sodium cyanide, thiocyanate and hydroxide, it is possible to prepare benzonitriles, benzyl thiocyanates and benzyl alcohols from the corresponding benzyl chlorides. Most of these reactions occur in yields of ca. 80%. 

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