Generation, isolation, and reactivity of a kinetically stabilized diphosphene anion radical

The stable lithium diphosphene anion radical, [Li(dme)3]+[TbtPPTbt]radical dot− (dme: 1,2-dimethoxyethane, Tbt: 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl), was readily synthesized by the one-electron reduction of the corresponding neutral diphosphene (TbtPdouble bond; length as m-dashPTbt). The molecular structure of the diphosphene anion radical was discussed in detail on the basis of its ESR, UV–Vis and Raman spectra, and theoretical calculations. The diphosphene anion radical was found to undergo ready chalcogenation reactions using elemental sulfur and selenium to afford the corresponding thiadiphosphirane and selenadiphosphirane, respectively.