Hypervalent Organoselenium(H) Compounds with Organophosphorus Ligands. Crystal and Molecular Structure of [2-(iPr2NCH2)C6H4]Se[S2PR′2] (R′ = Ph, OiPr)

Redistribution reactions between diorganodiselenides of type [2-(R2NCH2)C6H4](2)Se-2 [R = Et, iPr] and bis(diorganophosphinothioyl disulfanes of type [R'P-2(S)S](2) (R = Ph, OiPr) resulted in the hypervalent [2-(R2NCH2)C6H4]SeSP(S)R'(2) [R = Et, R' = Ph (1), OiPr (2); P. = iPr, R' = Ph (3), OiPr (4)] species. All new compounds were characterized by solution multinuclear NMR spectroscopy (H-1, C-13, P-31, Se-77) and the solid compounds 1, 3, and 4 also by FT-IR spectroscopy. The crystal and molecular structures of 3 and 4 were determined by single-crystal X-ray diffraction. In both compounds the N(1) atom is intramolecularly coordinated to the selenium atom, resulting in T-shaped coordination arrangements of type (C,N)SeS. The dithio organ-phosphorus ligands act monodentate in both complexes, which can be described as essentially monomeric species. Weak intermolecular S center dot center dot center dot H contacts could be considered in the crystal of 3, thus resulting in polymeric zig-zag chains of R and S isomers, respectively.