Synthesis, structure, and stability of a set of C-stereogenic heteroditopic P, S ligands.

• Preparation and characterization of a set of C-stereogenic P, S ligands is reported. • Corresponding S, S and S, Se ligands can be obtained by oxidation of the phosphanes. • Au(I) coordination occurs exclusively at the phosphane or phosphorane units. • Aurophilic interactions are observed with the selenophosphorane ligand exclusively. This study focuses on synthesis and investigation of coordination modes of phosphorus and sulfur-containing C-stereogenic compounds, prepared from thioanisole. Isolation of the C-stereogenic organolithium compound [RR'CHLi · 2THF] 2 (R = C 6 H 5 S, R' = (CH 3) 3 Si, THF = tetrahydrofuran) instead of in situ usage turned out to be mandatory for controlled reactivity. Variation of the steric and electronic properties of the substituents at phosphorus furnished three different phosphane substituted P, S ligands RR'CHPPh 2 , RR'CHP(N(C 2 H 5) 2) 2, and RR'CHP(t- C 4 H 9) 2. Furthermore, the corresponding chalcogenphosphoranes were synthesized by oxidation with elemental sulfur and selenium. Preliminary investigation of the coordination behavior of RR'CHP(t- C 4 H 9) 2 , RR'CHP(S)(t- C 4 H 9) 2 and RR'CHP(Se)(t- C 4 H 9) 2 towards coinage metals was explored with Au(tht)Cl, both for the phosphanes and the corresponding phosphoranes. Intermolecular aurophilic interactions have been observed for the selenophosphorane exclusively. Sequential lithiation and silylation of thioanisole leads to a C-stereogenic organolithium compound which has been employed to construct a set of C-stereogenic heteroditopic P, S ligands. Their coordination behavior towards Au(I) was explored as well as their reactivity with respect to chalcogens. [Display omitted] [ABSTRACT FROM AUTHOR]