Phosphines alkali phosphides

As well as for the preparation of alkali phosphides, the reaction of phosphine with the elements, their oxides or halides, at higher temperatures in quartz tubes have been much used recently for the preparation of other phosphides, in particular those which play important roles in semi-conductor technology. The preparations of the following phosphides using these methods have been described for example, NdP 3s> 36) 3p 137,138) Q p 139.140) SmP, LaP 136,141) TiP, Ti2P (possibly TisP) and InP See also Section IV.9. 

For alkylation of phosphines containing C-H bonds their alkali salts are usually treated with alkyl halides. Thus primary and secondary phosphines can be obtained by metalation of phosphine itself with sodium in liquid ammonia and subsequent alkylation 208 phosphirane, which is unstable, is also prepared in this way, from sodium phosphide and ethylene dichloride.209 High yields of primary phosphines are afforded by alkylating lithium phosphide, which is formed almost quantitatively by metalating phosphine with butyl-lithium.210 Since the hydrogen can be replaced stepwise by metal, unsymmetrical secondary and tertiary phosphines can be built up from PH3 or a primary phosphine.211 Use of alkali phosphides is not limited to alkylation potassium diphenylphosphide reacts quantitatively with iodobenzene, yielding triphenyl-phosphine.212... 

Aromatic phosphines that are difficult to obtain by other methods can be prepared by heating alkali phosphides with arenesulfonic acid salts, best in ethylene glycol ethers ... 

Preparation of Phosphines from Metallated Phosphines. - Alkali metal-free phosphide anions have been shown to be formed under synthetically useful conditions in the equilibria between primary or secondary phosphines with the Schwesinger bases (23). Techniques have been developed for the preparation of alkali metal diphenylphosphide reagents in high purity, as evidenced by P nmr studies. The same paper reports a study of the course of the reactions between potassium diphenylphosphide and a series of aryl-, n-alkyl- and neopentyl-halides. The results provide the first evidence of the involvement of single electron transfer (SET) processes in the reactions of alkyl halides. This pathway is dominant in the case of neopentyl-type iodides, but plays only a minor role in the related reactions of neopentyl-type bromides and chlorides. No evidence was adduced of the involvement of SET processes in the reactions of unhindered... 

The bis-hydrazidoyl chloride LXI, on treatment with the alkali phosphides LXII yields the bis-phosphine LXIII ( ). 

The methylsilyl phosphines are obtainable in reasonable yields by reacting chloromethylsilanes with lithium or other alkali phosphides (9.190-9.192). The tris derivative is also obtained by reaction (9.193). 

Sulfonimidophosphonates Phosphides s. Alkali phosphides Phosphinaminoboranes 16, 374 Phosphine, reactions with aldehydes, aliphatic 16, 696 —, reductions with — 17, 346 Phosphine boranes... 

Phosphides are binary compounds containing anionic phosphorus (P ). Heavy metal, alkali, and alkaline earth metal phosphides exist but few of them are commercially important. Phosphides hydrolyze to the flammable and toxic gas phosphine (PH3). The hydrolysis reaction of aluminum phosphide is given below ... 

Preparation of Phosphines from Metallated Phosphines.- It has been shown that phosphide anions may be generated from primary and secondary phosphines under aqueous conditions using concentrated aqueous alkali in DMSO or other dipolar aprotic solvents. 

The heavier alkali metal phosphides M P(SiMe3)2 (M = K, Rb, Cs) have been synthesized by P-Si cleavage of the corresponding trisilyl-phosphine with MOBu1 and have been structurally characterized as their THF adducts [M P(SiMe3)2 (THF)]x (21). The greater size of the... 

The reaction of alkali metal phosphides with appropriate halides, sultones or cyclic sulfates is a generd method for preparation of a variety of tertiary phosphines useful in aqueous organometallic catalysis. These... 

By far the most ubiquitous intermediates in synthesis of this class of phosphines are the alkali metal phosphides which can be prepared by either the KOH/DMSO method, by reaction of tertiary phosphines or chlorophosphines with alkali metals, or in the reaction of BuLi with appropriate secondary or tertiary phosphines. A number of the ligands in Figures 6 and 7 were prepared this way (60-69,72-74). 

Reaction with Phosphorus Nucleophiles. The ethyleneimine ring can be opened using phosphines (91) or alkali metal phosphides (92) ... 

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