Silyl and Related Phosphines

Silyl and Related Phosphines.—number of routes to the silylphosphines (4) and 

Quite the most unusual reaction of this year s literature is the formation of the phospha-alkenes (65) from the bis(trimethylsilyl)phosphines (66) and pivaloyl chloride. The monoacylphosphines (67) have been shown to be intermediates, and 

Diphenyl(trimethylsilyl)phosphine (4) reacts with the trifluorophosphorane (68) to produce the corresponding monofluorophosphine (69). Trisilylphosphine (70) 

A further study of germylphosphines by the French group has included the preparation of a series of 1,2-germaphospholans (73). The weak Ge—P bond is readily 

Couret, J. Escudie, J. Satg6, and G. Redoul s, Synth. React. Inorg. Metal-Org. Chem., 1977, 

Silyl- and Related Phosphines.—A new preparation of tris(trimethylsilyl)phosphine (61) from white phosphorus has been reported.62 Lithium derivatives of (61) may be prepared by cleavage with butyl-lithium,63 using glyme as solvent. 

Dimethyl(trimethylsilyl)phosphine (63) reacts with aluminium chlorides with cleavage of the silicon-phosphorus bond,58 as shown for aluminium trichloride. The same phosphine (63) reacts with the cobalt derivative (64) as shown.59 

Diacylphosphines may be prepared by treatment of bis(trimethylsilyl)phenyl-phosphine (65) with acid chlorides.60 A diphosphine derivative (66) is formed with benzoyl chloride.60 A series of complex reactions occurs between nitrobenzenes and diphenyl(trimethylsilyl)phosphine (67).61 The oxides noted below were the only isolable products, and the yields were not high.61 

Carbonyl-addition reactions continue to be the speciality of the French group interested in germylphosphines. Thus the germaphospholan (68) adds to aldehydes to give diastereomeric products (69).62 Steric factors are believed to control the mode 

Addition reactions of silylphosphines to imines have been reported, 4 as illustrated for diethyl(trimethylsilyl)phosphine (70). Organic azides react with germylphosphines by an insertion pathway,65 as shown for various phenyl(trimethylgermyl)phosphines (71). The initial products (72) isomerize to phosphine imines on heating.66 

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