Carbon amide phosphide

Phosphoms trichloride and pentachloride form sodium chloride and sodium phosphide, respectively, in the presence of sodium. Phosphoms oxychloride, POCl, when heated with sodium, explodes. Carbon disulfide reacts violendy, forming sodium sulfide. Sodium amide (sodamide), NaNH2, is formed by the reaction of ammonia gas with Hquid sodium. SoHd sodium reacts only superficially with Hquid sulfur dioxide but molten sodium and gaseous... 

During the cross-couplings to form C—N, C—O, C—S, and C—P bonds, the arylpalladium halide complexes are converted to arylpalladium amide, alkoxide, thiolate, and phosphide complexes. Examples of each type of complex have now been isolated, and the reductive elimination of the organic products has been studied. Although the reductive elimination to form carbon-hydrogen and carbon-carbon bonds is common, reductive elimination to form carbon-heteroatom bonds has been studied only recently. This reductive elimination chemistry has been reviewed.23... 

For vinylacetylene the static CNDO/2 data given in Figure 6 indicate that the two internal carbons are more electrophilic than the terminal ones but terminal attack is presumably favoured because this leads to transition states which are resonance-stabilized > . The confusing issue in the additions to vinylacetylene is the variability in the point of entry with changes in nucleophile and solvent, e.g. thiols attack primarily at the terminal sp carbon - - while alkoxides, phosphides and amides prefer the terminal sp- carbon . Attack on the internal sp carbon may occur when the vinylacetylene contains special substituents , e.g. equation (36). Perhaps these matters would be clarified if equilibrium and rate studies were performed. 

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