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Hypercoordinated triaryltelluronium compounds of type [{2-(Me2NCH2)C6H4}3Te]+L [L = (SPMe2)2N (1), (OPPh2)2N (2), (SPPh2)2N (3), (SPPh2){OP(OEt)2}N (4), (SPPh2)(O2SMe)N (5) and {SP(OEt)2}(O2SC6H4Cl-4)N (6)] were prepared by salt metathesis reactions between [{2-(Me2NCH2)C6H4}3Te]Cl•H2O and the potassium salts of the corresponding organophosphorus ligands in a 1:1 molar ratio. Multinuclear NMR spectroscopy, mass spectrometry, molar conductivity and IR spectroscopy were used to characterize the new complexes. The 1H NMR spectra suggest for all compounds the intramolecular coordination of the nitrogen atoms from the pendant arms to tellurium in solution. For compound 3 single-crystal X-ray diffraction studies revealed strong N→Te intramolecular interactions in solid state, which result in hypercoordinated triaryltelluronium(IV) cations (14‒Te‒6 species) with a distorted octahedral coordination geometry around tellurium. Weak S⋅⋅⋅H interactions between anions and cations resulted in a 2D supramolecular network.

The compound [2,6-(Me2NCH2)2C6H3]Hg(OAc) (1) was prepared by direct mercuration of 1,3-(Me2NCH2)2C6H4 with Hg(OAc)2. Treatment of 1 with excess of LiCl resulted in isolation of the chloride [2,6-(Me2NCH2)2C6H3]HgCl (2) in a good yield. The IR spectroscopy confirms the presence of the acetate group in 1. Both compounds 1 and 2 were characterized by solution multinuclear (1H, 13C and 199Hg) NMR spectroscopy and mass spectrometry. Their crystal and molecular structures were established by single-crystal X-ray diffraction. Different intermolecular interactions, i.e. Hg···Hg, O···Hg and C‒H···π (Arcentroid), were found for both compounds in solid state resulting in dimer or chain polymer associations.