Organoselenium(II) complexes containing organophosphorus ligands. Crystal and molecular structure of PhSeSP(S)Ph_2, [2-{MeN(CH_2CH_2)2NCH_2}C_6H_4]SeSP(S)R0_2 (R0 = Ph, OPr~i) and [2-{O(CH_2CH_2)2NCH_2}C_6H_4]SeSP(S)(OPr~i)2

摘要

Arylselenium(II) derivatives of dithiophosphorus ligands of type ArSeSP(S)R_2 [Ar = Ph, R = Ph (1), OPri (2);2-[MeN(CH_2CH_2)2NCH_2]C_6H_4, R = Ph (3), OPri (4); 2-[O(CH_2CH_2)2NCH_2]C_6H_4, R = OPri (6)] were prepared by redistribution reactions between Ar_2Se_2 and [R_2P(S)S]2. The derivative [2-{O(CH_2CH_2)2NCH_2}-C_6H_4]SeSP(S)Ph_2 (5) was obtained by the salt metathesis reaction between [2-{O(CH_2CH_2)2NCH_2}C_6H_4]-SeCl and NH_4S_2PPh_2. The compounds were investigated by multinuclear (1H, ~(13)C, ~(31)P, ~(77)Se) NMR and infrared spectroscopy. The crystal and molecular structures of 1, 3, 4 and 6 were determined by single-crystal X-ray diffraction. In compounds 3, 4 and 6 the N(1) atom is intramolecularly coordinated to the selenium center, resulting in a T-shaped geometry (hypervalent 10-Se-3 species). The dithiophosphorus ligands act as anisobidentate in 1 and monodentate in 3, 4 and 6. Supramolecular architectures based on intermolecular S...H and N...H contacts between molecular units are formed in the hypervalent derivatives 3 and 4, while in the compounds 1 and 6 the molecules are associated into polymeric chains through either Se...S or O...H contacts, with no further inter-chain interactions.