Band 36, Heft 1-2

We analyzed and classified almost 100 heterotrimers of platinum with non-transition metals of the composition Pt 2 M (42 examples), PtM 2 (48 examples), and PtMM' (6 examples). These trimers crystallized in five crystal classes: rhombohedral and tetragonal, each 1.5%; orthorhombic, 4%; triclinic, 35%; and monoclinic, 58%. There are 15 non-transition metals: Ge, Sn, Pb, Zn, Cd, Hg, Li, Na, K, Ga, In, Tl, Al, Sb, and Bi, which are partners to Pt for the creation of their respective heterotrimers. The three metal atoms form a wide variety of frameworks, with triangular and linear the most common. There is a rich variety of Pt-M bond lengths, with the mean values following the order: 2.326 Å (M=Al)<2.351 Å (Ga)<2.450 Å (Ge)<2.549 Å (Sn)<2.560 Å (Sb)<2.562 Å (In)<2.582 Å (Li)<2.658 Å (Hg)<2.738 (Pb)<2.770 Å (Tl). In the series Pt 2 M, the mean Pt-Pt bond distance is 2.803 Å. Correlations between structural parameters, heterometals, and donor ligands were developed and discussed.

The synthesis of [Bi 38 O 45 (OMc) 22 (C 8 H 7 SO 3 ) 2 (DMSO) 6 (H 2 O) 1.5 ]·2.5H 2 O ( 1 ·2.5H 2 O) (OMc—methacrylate) and [Bi 38 O 45 (HSal) 22 (OMc) 2 (DMSO) 15 (H 2 O)]·DMSO·2H 2 O( 2 ·DMSO·2H 2 O) (Hsal—salicylate) starting from [Bi 38 O 45 (OMc) 24 (DMSO) 9 ]·2DMSO·7H 2 O and sodium 4-vinylbenzenesulfonate and salicylic acid, respectively, is presented. The bismuth oxido clusters show diameters of 2.9 nm ( 1 ) and 2.4 nm ( 2 ) and molecular weights of 11,440.22 g/mol ( 1 ·2.5H 2 O) and 13,151.92 g/mol ( 2 ·DMSO·2H 2 O). The polynuclear framework of 1 and 2 is quite similar; nevertheless, a comparison of the bismuth and oxygen atom positions of 1 and 2 shows a weighted root mean square deviation of 0.307 and 0.413 Å, respectively, as a result of the different coordination sphere. Both [Bi 38 O 45 ] 24+ cores in 1 and 2 are coordinated by two different anionic ligands with a ligand-to-ligand ratio of 22:2, which might indicate two particularly reactive positions at each bismuth oxido cluster.

Treatment of [{ D (C 6 H 4 S) 2 }SbCl] ( D =O, 1 ; D =S, 2 ) with MS 2 P(OR) 2 afforded the stable dibenzostibocine dithiophosphate compounds [{ D (C 6 H 4 S) 2 }Sb{S 2 P(OR) 2 }] with D =O, R=1,2-C 6 H 4 ( 3 ); for D =S, R=1,2-C 6 H 4 ( 4 ), Et ( 5 ), n Pr ( 6 ), i Pr ( 7 ), and Ph ( 8 ). The compounds were characterized by IR and 1 H, 13 C{ 1 H}, and 31 P{ 1 H} NMR spectroscopy in solution. The 31 P{ 1 H} NMR data are consistent with an anisobidentate coordination mode of the dithiophosphate ligand to the Sb atom. Single crystal X-ray diffraction analyses of compounds 3 , 4 , 7 , and 8 revealed that the antimony atom acts as an acceptor atom exhibiting endocyclic and exocyclic intramolecular interactions with the donor D atom and with both sulfur atoms of the dithiophosphate ligand, expanding its coordination sphere from four in the starting materials to five and displaying a skew-trapezoidal pyramidal local geometry.

Four new phenylphosphonato SnR 3 (R=Ph, Me) derivatives have been synthesized and characterized by infrared and Mössbauer spectroscopy. The structure of catena-poly[PhPO 3 HSnMe 3 ] n has been determined by single-crystal X-ray diffraction analysis. The Sn IV atoms are five-coordinated in all compounds, with the SnC 3 O 2 framework in a trans trigonal bipyramidal arrangement and the PhPO 3 H - anions being in axial positions. The molecular structure of [PhPO 3 HSnMe 3 ] n is arranged as a one-dimensional coordination polymer in which planar SnMe 3 groups are axially bridged by -O-P-O- linkages of the PhPO 3 H - ligand. Neighboring chains are linked via O-H ∙∙∙ O hydrogen bond interactions, generating a layered structure. In the R 2 NH 2 (PhPO 3 H) 2 SnR′ 3 (R=Cy, Bu; R′=Ph, Me), the SnPh 3 or SnMe 3 residue is axially coordinated by two monodentate PhPO 3 H - . The role of the dialkylammonium cation, R 2 NH 2 + , is crucial in the lattice building via a hydrogen bond network. These hydrogen bonds contribute to the crystal stability and compactness and result in a three-dimensional arrangement. The aqua complex PhPO 3 (SnPh 3 ) 2 ·2H 2 O has a discrete structure and the anion PhPO 3 2- behaves as a bidentate ligand.

The synthesis, by green methodology using microwaves, of the novel Schiff base LH derived from o -vanillin and acetazolamide and of the corresponding organotin derivatives R 2 SnL 2 (1, R= n -Bu; 2, R= n -Oct) and n -Bu 3 SnL (3) is reported. The compounds are characterized by elemental analyses; 1 H, 13 C, and 119 Sn NMR; IR; and UV-vis spectroscopy.

A new series of silicon(IV) complexes have been synthesized by adopting classical thermal- and microwave-irradiated techniques. The complexes are prepared by the reaction of dimethyldichlorosilane and triphenylchlorosilane with the sodium salts of 1-(1-(2-oxo-2H-chromen-3-yl)ethylidene)thiosemicarbazide and 1-(1-(2-oxo-2H-chromen-3-yl)ethylidene)semicabazide in 1:1 and/or 1:2 molar ratios. Characterization of the ligands as well as of the silicon complexes has been carried out on the basis of elemental analysis, melting point determinations, molecular weight determinations, infrared, 1 H NMR, 13 C NMR, 29 Si NMR, and electronic and mass spectral studies. Spectral studies confirm ligands to be monofunctional bidentate and trigonal bipyramidal and octahedral environments around silicon ions. The newly synthesized ligands and their complexes have been screened for antimicrobial, minimum inhibitory concentration, and pesticidal activities. The results obtained from bioassays indicate that this class of compounds can be utilized for the design of new substances with pesticidal activity and promising antimicrobial activity.

Diorganotin(IV) and triorganotin(IV) derivatives of the types R 2 SnA (R= n -Bu and n -octyl) and (R 3 Sn) 2 A (R= n -Bu), where A is the anion of albendazole {methyl[(5-propylsulfanyl-3 H -benzoimidazol-2-yl) amino]formate}, ofloxacin {( RS )-7-fluoro-2-methyl-6-(4-methylpiperazin-1-yl)-10-oxo-4-oxa-1-azatricyclo[7.3.1.0 5,13 ] trideca-5(13),6,8,11-tetraene-11-carboxylicacid} and 3-carboxypropyldisulfide, have been synthesized. The complexes 1 – 9 obtained were characterized by elemental analysis as well as infrared (Fourier transform infrared), nuclear magnetic resonance ( 1 H, 13 C and 119 Sn NMR) and ultraviolet spectroscopy. On the basis of these spectroscopic studies it was proposed that diorganotin complexes of 3-carboxypropyldisulfide having 1:1 stoichiometry and complexes of albendazole and ofloxacin having 1:2 stoichiometry show tetrahedral geometry around the tin atom with monodentate behavior of the carboxylate group in ofloxacin and 3-carboxypropyldisulfide. Triorganotin complexes of 3-carboxypropyldisulfide having 1:1 stoichiometry and complexes of ofloxacin and albendazole having 1:2 stoichiometry show trigonal bipyramidal geometry. The ligand molecule is bound to the Sn atom through carboxyl oxygen atoms in ofloxacin and 3-carboxypropyldisulfide, and to the nitrogen atom in albendazole. The biological activity of the synthesized complexes 4 , 5 and 6 has been screened against Candida albicans .

The title compound Mes 2 TeCl 2 crystallises from CHCl 3 as colourless plates and needles that turned out to be triclinic and monoclinic modifications. Both polymorphs have been investigated by X-ray crystallography. The molecular structures are very similar. Crystal packing effects have only a marginal influence on the structural parameters.