Gas-phase molecular structures of bis(difluorothiophosphoryl)-methane, CH2(PF2S)2, and bis(difluorothiophosphoryl) ether, O( PF2S)2, determined by electron diffraction

Abstract

The molecular structures of the compounds bis(difluorothiophosphoryl)methane, CH₂(PF₂S)₂, and bis(difluorothiophosphoryl) ether, O(PF₂S)₂, have been determined by electron diffraction. The methane derivative has two conformers, gauche-gauche and anti-gauche, present in approximately equal amounts. Other important parameters (r_a) are r(P–C) 180.7(7), r(PS) 187.9(3), r(P–F) 154.8(2) pm; FPF 101.8(7), FPC 103.2(4), SPC 115.0(10), and PCP 122.6(10)°. For the ether, all PF₂S groups have gauche conformations, but it was not possible to distinguish overall C₂ and C_S structures. For the best refinements, important parameters are r(P–O) 161.0(8), r(PS) 186.5(5). r(P–F) 152.6(3) pm; FPF 101.9(47), FPO 100.2(24), SPO 116.5(33), and POP 130.9(35)°.