Structure and Reactivity of Esters of Thio-acids of Three-coordinated Phosphorus

The structure and the chemical behaviour of thio-esters of three-coordinated phosphorus R_nP(SR')_3–n (n = 0–2) are examined, and their reactions are discussed with electrophilic reagents differing both in the number and in the nature of the electrophilic centres. The peculiar character of such reactions is due primarily to the presence of two competing nucleophilic centres to the ambidenticity of the phosphorus(lll)–sulphur(ll) group, and to the high reactivity of two-coordinated sulphur (thionic and thiolic) in esters of three- and four-coordinated phosphorus. A list of 170 references is included.