TriAmide, phosphoryl thiophosphoryl

Amorphous polymeric materials with composition (PON) and (PSN) can be obtained from reactions of NHj with POCI3 and PSCI3, respectively. With more limited reactions, phosphoryl triamide or thiophosphoryl triamide (7.48) can be made. These compounds are colourless crystalline solids which are soluble in water, but the action of heat will eventually transform them into (PON) and (PSN) . The polymeric oxynitride can be made crystalline by heating to 700°C under pressure. 

Thiophosphoryl triamide is prepared in a manner analogous to that of phosphoryl triamide, involving the reaction of ammonia with thiophosphoryl trichloride in chloroform while cooling 1... 

Arguments have been presented to suggest that the mechanism of catalyzed nucleophilic displacement at a phosphoryl or thiophosphoryl centre may not be as had been previously thought. Thus far, nucleophilic displacements have been thought to involve double Sj 2 displacements involving the catalyst and/or, pentacoordinate intermediates. Measurements of reaction rates and stereochemical changes for a variety of linear and cyclic phosphorochloridates (and also phosphonochloridates and phosphonochloridothioates) in alcoholysis reactions catalyzed by hexamethylphosphorous triamide, pyridine, or N-methylimidazole (the order of increasing reactivity) have been used to question the earlier ideas, and it has now been proposed that the... 

I. Thiophosphoryl triamide is obtained similarly to phosphoryl triamide (see p. 584) via reaction of NH3 and PSCI3 in chloroform solution. The reaction flask must be well cooled (Klement and Koch) ... 

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