Addressing the Nature of Phosphinidene Sulfides via the Synthesis of P−S Heterocycles

The phosphorus-sulfur heterocycles 1,2-thiaphosphetenes and phosphirene sulfides have been prepared, and represent the first structurally characterized derivatives for either class of compound. These strained P-S ring systems are formed by the reaction of a phosphinidene sulfide and alkyne. Using an internal alkyne, only the 3-membered PV , phosphirene sulfide was produced, whereas a terminal alkyne yielded a mixture of phosphirene sulfide and 1,2-thiaphosphetene (PIII ). Detailed computational analysis revealed that for numerous derivatives of alkynes, the corresponding 4-membered rings are always more stable than the 3-membered isomers. The electronic nature of "free" phosphinidene sulfides (R-P=S) is discussed based on computational results.