Molecular structures of Se(SCH3)2 and Te(SCH3)2 using gas-phase electron diffraction and ab initio and DFT geometry optimisations

Abstract

The molecular structures of Se(SCH₃)₂ and Te(SCH₃)₂ were investigated using gas-phase electron diffraction (GED) and ab initio and DFT geometry optimisations. While parameters involving H atoms were refined using flexible restraints according to the SARACEN method, parameters that depended only on heavy atoms could be refined without restraints. The GED-determined geometric parameters (r_h1) are: rSe–S 219.1(1), rS–C 183.2(1), rC–H 109.6(4) pm; ∠S–Se–S 102.9(3), ∠Se–S–C 100.6(2), ∠S–C–H (mean) 107.4(5), ϕS–Se–S–C 87.9(20), ϕSe–S–C–H 178.8(19)° for Se(SCH₃)₂, and rTe–S 238.1(2), rS–C 184.1(3), rC–H 110.0(6) pm; ∠S–Te–S 98.9(6), ∠Te–S–C 99.7(4), ∠S–C–H (mean) 109.2(9), ϕS–Te–S–C 73.0(48), ϕTe–S–C–H 180.1(19)° for Te(SCH₃)₂. Ab initio and DFT calculations were performed at the HF, MP2 and B3LYP levels, employing either full-electron basis sets [3-21G(d) or 6-31G(d)] or an effective core potential with a valence basis set [LanL2DZ(d)]. The best fit to the GED structures was achieved at the MP2 level. Differences between GED and MP2 results for rS–C and ∠S–Te–S were explained by the thermal population of excited vibrational states under the experimental conditions. All theoretical models agreed that each compound exists as two stable conformers, one in which the methyl groups are on the same side (g⁺g⁻ conformer) and one in which they are on different sides (g⁺g⁺ conformer) of the S–Y–S plane (Y = Se, Te). The conformational composition under the experimental conditions could not be resolved from the GED data. Despite GED R-factors and ab initio and DFT energies favouring the g⁺g⁺ conformer, it is likely that both conformers are present, for Se(SCH₃)₂ as well as for Te(SCH₃)₂.