Free monomeric thiometaphosphate in protic solvents: complete racemisation at phosphorus in the ethanolysis of 4-nitrophenyl thiophosphate

Abstract

The ethanolysis of the monoanion of R_P-4-nitrophenyl [¹⁸O]thiophosphate (1) proceeds with a large degree of racemisation (ca. 80%) and the dianion with complete racemisation, the corresponding solvolysis of the monoanion in aqueous ethanol giving ethyl thiophosphate (3) with ca. 70% racemisation; these data provide the first direct support of a freely-solvated monomeric thiometaphosphate intermediate (2) in the case of the solvolysis of the dianion in ethanol and a relatively long-lived intermediate for the monoanion in ethanol and in aqueous ethanol.