On Mercury(I) Oxo Compounds — Quasi‐Relativistic Computational and Experimental Studies

About 60 molecular species composed of up to 10 mercury atoms and of oxygen atoms and/or of some other elements or groups (such as halogen, OH₂, OH, H, alkali, NO₃) have been investigated quantum chemically. Different density functional approaches and the ab initio SCF‐MP2 method were applied, comparing different basis sets and different atomic core sizes. It is important not to treat the Hg 5s, p, d as inactive core shells, and to use sufficiently many polarization functions. The shape of the 〉O‐Hg‐Hg‐O〈 units is not favorable concerning the formation of lattices composed of Hg^I, O and OH only. Despite its bulkiness, the OHgHgO units can easily come into contact with each other and then disproportionate. This is prevented in the so‐called ternary M‐Hg^I oxides by the embedded oxometallate (oxoacidic) anions. Furthermore, the Hg^I and Hg^II oxide bond energies are less favorable towards the stability of Hg^I oxo compounds, as compared to Hg halidic or oxoacidic compounds. Both points are not promising concerning the search for Hg^I oxides/hydroxides, although the preparation of such compounds, including spacer groups, by topochemical reactions can still not be excluded. So far, experimental efforts towards the synthesis of such a new class of compounds have only demonstrated that Hg^II is strictly preferred over Hg^I in the formation of solids of binary Hg‐O or ternary A‐Hg‐O composition (A = electropositive metal such as alkali, in contrast to M = transition or semi‐metal). This is so even if compounds containing ‘electron rich Hg^δ— atoms’ (i.e. A‐Hg amalgams) are oxidized under mild conditions.     

Influence of the texture of chromia catalysts on their activity in synthesis of 2-methylthiophene

The texture of Cr₂O₃-K₂O/Al₂O₃catalysts containing oxides of rare earth elements (REE) was studied. The catalysts are used for the synthesis of 2-methylthiophene by the reaction of H₂S with n-pentane or piperilene. The heterocyclization of n-pentane is a consecutive reaction involving a step of dehydrogenation of initial hydrocarbon. At this step the texture of the catalyst affects the yield of 2-methylthiophene. The yield of 2-methylthiophene obtained from piperilene and I₂S is independent of the catalyst texture.     

Preparation of Mn3O4 nanocrystallites by low-temperature solvothermal treatment of γ-MnOOH nanowires

The preparation of trimanganese tetroxide (Mn₃O₄) nanocrystallites from γ-MnOOH nanowires under mild conditions has been achieved by two steps: first, γ-MnOOH nanowires with a mean diameter of about 12 nm and lengths of up to several micrometers were directly prepared via hydrothermal reaction between KMnO₄ and toluene in water at 180°C for 24 h; then, pure Mn₃O₄ nanocrystallites could be obtained by solvothermal treatment of the γ-MnOOH nanowires in ethylenediamine (EDA) and ethylene glycol (EG) at 150°C for 24 h. It was found that the Mn₃O₄ product obtained in EDA comprised well-defined nanocrystallites with the size in the range of 15-35 nm, while the one obtained in EG consisted of aggregated nanoparticles with the size of less than 18 nm.The possible formation mechanism of nanocrystalline Mn₃O₄ in EDA and EG and reasons for the different effects of various solvents on the products were also proposed.     

Synthesis, Characterisation and UV-Vis Properties of Azocalix[4]crowns

This article describes the synthesis, structure andUV properties of azocalixcrowns in which the photoresponsivetrans-cis azo benzene unit has been introduced in the glycolicchains of the calix[4]crowns. The synthesis proceeded via the selective-1,3O-dialkylation of calix[4]arene with glycolic chains terminated bynitrophenyl residues. After reduction of thenitro groups into amino functions,intramolecular oxidative coupling produced thecapping of the calixarene. Thesynthetic approaches and the cis-transstructure of these new ligandsare discussed and full details on synthesesand structural data are given. Apreliminary example of cesium complexation byone of the ligands is proposed.     

Molecular and crystal structures of ruthenium and osmium arene clusters

The molecular and crystal structures of a number of ruthenium and osmium clusters of nuclearity between three and six containing arene fragments such as C₆H₆, C₆H₃Me₃, C₆H₄Me₂ and C₆H₅Me have been investigated. Attention has been focused on the relationship between the terminal ( ⁶-coordination) and face-capping ( ₃: ²: ²: ²-coordination) bonding modes. Empirical packing potential energy calculations have been employed to investigate the intermolecular organization in the crystal. It has been shown that the arene fragments in mono-arene clusters form ribbons, while in bis-arene clusters graphitic-like interactions throughout the crystal are established. The factors controlling the ease of arene reorientational motion in the solid state has also been investigated in relation to the shape, size and geometry of the molecules and of their interlocking modes.     

Synthesis, structure and magnetic properties of the S=1/2, one-dimensional antiferromagnet, Y5Re2O12

Single crystals of Y₅Re₂O₁₂ have been grown, and the crystal structure has been determined by X-ray diffraction. This compound crystallizes in space group C2/m with cell dimensions of a=12.4081(10) Å b=5.6604(5)Å, c=7.4951(6) Å, β=107.837(3)°, Z=2. The final refinement led to R1=0.0238, WR2=0.0459 for 1053 observed reflections with F>4σ(F₀). Edge-sharing ReO₆ octahedra form infinite linear [ReO₂O_4/2]_n chains along the b direction with alternating short and long Re-Re distances. Three crystallographically independent yttrium atoms surround O2 to form OY₄ tetrahedra, which share edges and corners in the ab plane to form a two-dimensional Y₅O₄ network which separates the [ReO₂O_4/2]_n magnetic chains. This compound is therefore isostructural with the series Ln₅Re₂O₁₂Ln=Gd-Lu, which have been known since 1969. The average Re oxidation state is +4.5 in the chains and a reasonable, if qualitative MO scheme results in one unpaired electron per Re dimer. Consistent with this, magnetic susceptibility data can be fitted to the one-dimensional antiferromagnetic Heisenberg model with S=1/2 and parameters J^intra/k=−89(1)K, g=2.15(4) and χ(TIP)=5(1)×10⁻⁴ emu/mol. There is no sign of long-range magnetic order down to 2 K. These results are contrasted with those for the isostructural Y₅Mo₂O₁₂.     

Synthesis of calixarene-cyclodextrin coupling products

The coupling of two or four mono-6-amino β-cyclodextrin (amino-CD) units, (unprotected or permethylated hydroxyls), to diisopropoxycalix[4]arene crown-6 (CAL) was realised using the N,N′-succinyldiamide linker. The resulting molecules in two series were characterised with the help of mass and NMR spectroscopies. The yields of all coupling products were improved for permethylated sugar series compared to the hydroxylated CD series or to our previous studies. The two β-cyclodextrin (β-CD) residues coupled to disubstituted CAL were orientated from the same side of the crown ether.     

Novel reaction of 1-aryl-2-bromodiazene 1-oxides with olefins. Synthesis of 1-aryl-2-(2-bromoalkyl)diazene 1-oxides

The addition of 1-aryl-2-bromodiazene 1-oxides to olefins yields 1-aryl-2-(2-bromoalkyl)diazene 1-oxides (4). A radical mechanism of the reaction has been suggested. Compounds4 decompose to give bromohydrazones of formaldehyde and aldehydes. The structural factors that affect the rate of this process are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 917–923, May, 1995.The work was carried out in the Scientific Educational Center of the Institute of Organic Chemistry of the RAS with financial support of the Russian Foundation for Basic Research (Project No. 93-03-18461).     

Determination of Copper at a Glassy Carbon Electrode Modified with Langmuir–Blodgett Film of p‐tert‐Butylthiacalix[4]arene

A new type of voltammetric sensor, Langmuir–Blodgett film of p‐tert‐butylthiacalix[4]arene modified glassy carbon electrode, was advanced and used for determining copper at trace levels by differential pulse stripping voltammetry. Calibration plot was found to be linear in the range of 2×10^?8 M to 5×10^?6 M; the detection limit was 2×10^?9 M. Possible recognition mechanism was also discussed. From determination of Copper in real samples (river, lake and tap water) it can be concluded that the method is rapid, sensitive in determining of copper and can be used in the analysis of natural water samples.     

Formation of α-Mn2O3 nanorods via a hydrothermal-assisted cleavage-decomposition mechanism

A hydrothermal cleavage-decomposition mechanism was used to synthesize single-crystal α-Mn₂O₃ nanorods at 160 °C for 16 h using KMnO₄ as manganese source and CTAB as reducing regent. The as-synthesized products were characterized by powder X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy and infrared spectrum. The results indicate that the reaction temperature is a crucial factor for the formation of α-Mn₂O₃ nanorods. These nanorods exhibit single-crystal nature, and have an average diameter of 36 nm and lengths of up to 1 μm. Based on our experimental results, a hydrothermal cleavage-decomposition mechanism has been proposed on the formation of α-Mn₂O₃ nanorods.