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The diorganotin(IV) compound Ph2Sn(S2CNMe2)(NCS) (3) was obtained by reacting either Ph2Sn(SCN)2 (1) or Ph2Sn(S2CNMe2)Cl (2) with sodium dimethyldithiocarbamate, in a 1:1 molar ratio, in CH2Cl2. Multinuclear (1H, 13C and 119Sn) NMR spectroscopy and mass spectrometry were used to characterize the new complex. Single-crystal X-ray diffraction studies revealed a bidentate behaviour of the dithiocarbamato ligand and a monodentate coordination of the NCS moiety through its nitrogen atom, thus resulting in a pentacoordinated C2SnS2N core. A 3D supramolecular network built through weak intermolecular S∙∙∙S and S∙∙∙H interactions was evidenced in the crystal of 3.

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.

Reaction of Ph3Bi[O(O)CC5H4N‐3]2 (1) in CHCl3 and AgClO4 in ethanol, in 1:1 molar ratio, afforded the isolation of colorless crystals of a coordination compound which was proved to be [Ag(EtOH){Ph3Bi[O(O)CC5H4N-3]2}(ClO4)]•CHCl3 (2•CHCl3) by single-crystal X-ray diffraction. A 1D coordination polymer is formed based on bridging triphenylbismuth(V) di(nicotinate) between silver atoms, with trans Ag−N dative bonds [2.183(4), 2.196(5) Å]. Additional Ag•••O interactions are established between the coinage metal atom and an ethanol molecule [2.58(3) Å] as well as a perchlorate anion [2.746(6) Å], respectively. Its supramolecular architecture, based on a variety of non-covalent interactions, i.e. O−H•••O, C−H•••O or C−H•••Cl hydrogen bonds, π•••π , C−H•••π, C−Cl•••π interactions, as well as Ag•••O and Ag•••Cl contacts, is discussed.

Organobismuth chalcogenides of type [CH3OCH2CH2N(CH2C6H4)2Bi]2E [E = S (1), Se (2)], containing two butterfly-like tetrahydro-dibenzo[c,f][1,5]azabismocine heterocyclic frameworks, were prepared and their solution behavior was investigated by multinuclear NMR spectroscopy (1H, 13C and 77Se, as appropriate) and mass spectrometry. Crystals of [CH3OCH2CH2N(CH2C6H4)2BiO]2SeO (3) were serendipitously formed during the synthesis of compound 2. The molecular structure of 3 was determined by single-crystal X-ray diffraction and revealed, besides a strong transannular N→Bi interaction, an additional O‧‧‧Bi interaction involving the oxygen of the NCH2CH2OCH3 pendant arm from the organic fragment attached to the metal atom, thus resulting in a 12Bi5 hypercoordinate species.

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.