Volume 38, Issue 3-4

The amino-functionalised xanthate NaS 2 COC 2 H 4 N(Me)C 2 H 4 NMe 2 ( 1 ) was synthesised, and its structure was determined to be a coordination polymer incorporating a six-coordinate metal with S 3 N 2 O ligation and in which the ligand delivers κ 2 - S,S chelate, κ 2 - S,O chelate, κ 2 - N,N chelate, and μ 2 -S bridging modes. 1 has been used to prepare the copper complex (Ph 3 P) 2 CuS 2 COC 2 H 4 N(Me)C 2 H 4 NMe 2 ( 5 ), although reactions with various Zn(II) and Cd(II) salts yielded only the metal sulphide decomposition product and the free acid as its 1,1,4-trimethylpiperazinium salt ( 2 ). Attempts to insert CS 2 into the alkoxides RMOC 2 H 4 N(Me)C 2 H 4 NMe 2 (M=Zn, R=Et [ 3 ]; M=Cd, R=Me [ 4 ]) also failed to give the desired group 12 derivative of the amino-functionalised xanthate. The structures of 2 – 5 are also reported.

Hydrogenation of Cp*SiCl 2 SiCl 3 ( A ) (Cp*=C 5 Me 5 ) with diisobutylaluminum hydride (DIBAL-H) gave partially hydrogenated disilane Cp*SiCl 2 SiH 3 ( 1 ) with 45% yield, whereas the reaction with lithium aluminum hydride (LiAlH 4 ) provided the well-known Cp*SiH 2 SiH 3 . The symmetric disilane Cp*SiH 2 SiH 2 Cp* ( 2 ) is accessible either by hydrogenation of Cp*SiCl 2 SiCl 2 Cp* ( B ) with DIBAL-H or LiAlH 4 but attempts to partially hydrogenate the disilane B failed. The reaction of B with 1 eq. DIBAL-H afforded a mixture of five different molecules of the type Cp*SiR 1 R 2 SiR 3 R 4 Cp* ( D , R 1 -R 4 =H, Cl) which co-crystallize in a single crystal with a H/Cl ratio of 1/3. Characterization by 1 H and 29 Si NMR, ATR IR spectroscopy, EI mass spectrometry and for 1 and the co-crystal D the single crystal X-ray diffraction analysis is presented. Compounds 1 and 2 are thermally stable in the solid state and do not decompose prior to evaporation.

Gallium(III) complexes [Ga(chmdtc) 3 ] ( 1 ) and [Ga(chedtc) 3 ] ( 2 ) (where chmdtc=cyclohexylmethyldithiocarbamate and chedtc=cyclohexylethyldithiocarbamate) have been prepared and characterized by infrared, nuclear magnetic resonance ( 1 H and 13 C) spectra, thermogravimetry, X-ray photoelectron spectroscopy, and single crystal X-ray diffraction (XRD). The thermogravimetric curves obtained for both complexes are almost similar. The final residue corresponded to gallium sulfide (Ga 2 S 3 ) above 700°C for complexes ( 1 ) and ( 2 ). In the single crystal X-ray structure of [Ga(chedtc) 3 ] ( 2 ), Ga-S bonds, and the associated C-S bonds show asymmetry as a requirement of packing. The complex shows distorted octahedral geometry due to its bite angle variations. Nano-α-Ga 2 S 3 was prepared from single source precursors [Ga(chmdtc) 3 ] ( 1 ) and [Ga(chedtc) 3 ] ( 2 ). Prepared nano-Ga 2 S 3 have been characterized by powder XRD, energy-dispersive X-ray spectroscopy technique, and transmission electron microscopy (TEM)-selected area electron diffraction analysis showing the nano-sized nature of Ga 2 S 3 . TEM micrographs confirmed the size of the particles to be 50 nm.

Two organotin complexes of 2-phenyl-1,2, 3-triazole-4-carboxylic acid, {[ n -Bu 2 Sn(OOCC 2 HN 3 Ph-2)] 2 O} 2 ( 1 ) and ( c -C 6 H 11 ) 3 Sn(OOCC 2 HN 3 Ph-2)(C 2 H 5 OH) ( 2 ), have been synthesized and characterized by means of elemental analysis, FT-IR, NMR ( 1 H, 13 C and 119 Sn) spectra and X-ray single crystal diffraction. Compound 1 is a centrosymmetric tetranuclear bis(dicarboxylatotetra- n -butyldistannoxane) complex containing two distinct types of carboxylate moieties and tin atoms with [SnC 2 O 3 ] trigonal-bipyramidal and [SnC 2 O 4 ] skew-trapezoidal-bipyramidal geometries. Compound 2 possesses a [SnC 3 O 2 ] trigonal bipyramidal environment with the axial positions occupied by the carboxylate oxygen and hydroxyl oxygen of an ethanol molecule and forms a one-dimensional supramolecular structure by intermolecular O-H···O hydrogen bonds. Bioassay results have shown that the two compounds possess good in vitro cytotoxic activity against three human tumor cell lines (HeLa, CoLo205 and MCF-7).

Two [2-(( L )-menthoxycarbonyl)ethyl]diphenyltin halides, ( L )-MenOCOCH 2 CH 2 SnXPh 2 (X=Cl, 1 ; I, 2 ), have been synthesized and characterized by means of elemental analysis, FT-IR, NMR ( 1 H, 13 C, and 119 Sn) spectroscopy, and X-ray single crystal diffraction. The tin atoms in 1 and 2 are both five-coordinated and possess the [C 3 SnOX] (X=Cl and I) trigonal bipyramidal environment with the trigonal plane defined by the three carbon atoms and the axial positions occupied by the halogen atom and internal carbonyl oxygen. There is a five-membered chelate ring in 1 and 2 with the Sn-O distance being 2.4781(16) and 2.512(2) Å, respectively.

In the present study, magnesium borate synthesis was performed by a hydrothermal mixing method, with the use of magnesium waste scraps (W) as the magnesium source, along with boric acid (H) or boron oxide (B) as the boron source. For an environment-friendly approach, a solid waste of magnesium was used at low reaction temperatures. Results of X-ray diffraction analyses showed that admontite [MgO(B 2 O 3 ) 3 ·7(H 2 O)] and mcallisterite [Mg 2 (B 6 O 7 (OH) 6 ) 2 ·9(H 2 O)] types of magnesium minerals were obtained from the synthesis. Through Fourier transform infrared spectroscopy and Raman spectroscopy, in both the infrared and the visible regions, characteristic borate bands were observed. The results of the boron oxide content analyses were in agreement with literature data. The particle sizes, obtained by scanning electron microscopy analyses, were found within the range of 200 nm to 2 μm for mcallisterite and 210 nm to 2.5 μm for admontite minerals. The reaction yields of the minerals were calculated in the range of 16.6–82.0% for the experiments on waste magnesium and boric acid, whereas for the experiments on waste magnesium and boron oxide these were 12.7–78.8%.

A new one-dimensional coordination polymer [Pb(2,2 ′ -bipy)(Hsal) 2 ] n has been synthesized and characterized by means of elemental analysis, FT-IR, powder X-ray diffraction, and X-ray single-crystal diffraction, where Hsal is salicylate, 2,2′-bipy is 2,2′-bipyridine. The compound consists of a one-dimensional chain, which was linked by C-H···π interactions and intermolecular C-H···O hydrogen bonds, therefore two-dimensional network was obtained.

Heterobimetallic thiolate [Cu(PPh 3 )] 4 (ZnCl) 2 (SEt) 6 has been synthesised and characterised by X-ray crystallography as a THF solvate. It contains the first structurally characterised example of a Cu I -S(R)-Zn II linkage and only the second species type to embody the Cu I -S-Zn II triad.

Mercury (Hg) has a long history of both medicinal uses and toxic effects. Hg chlorides were used as medicines; however, ‘corrosive sublimate’ (HgCl 2 ) was also used as a violent poison in the Middle Ages. In this work, certain thermodynamic principles of reactivity were used to show that ingested aqueous calomel (Hg 2 Cl 2 ) in the human stomach is almost entirely converted to HgCl 2 . This work opens the way to a new series of studies on poisoning cases in history.