Sesquialkoxide von Gallium und Indium

Sesquialkoxides of Gallium and Indium Treatment of GaMe₃ with one equivalent of HO^cHex in toluene at 20 °C leads to [Me₂GaO^cHex]₂ ( 4 ) under evolution of methane. The reaction of InMe₃ with two equivalents of HO^cHex leads under similar conditions not to [MeIn(O^cHex)₂]_n but to the sesquialkoxide [In{Me₂In(O^cHex)₂}₃] ( 5 ). 5 can be described also as [{Me₂InO^cHex)}₂{MeIn(O^cHex)₂}₂]. The use of an excess of cyclohexanol in boiling toluene gives the same result. Under these reflux conditions, the reaction of GaMe₃ with an excess of PhCH₂OH leads exclusively to another type of sequialkoxides, [Ga{MeGa(OCH₂Ph)₃}₃] ( 6 ). 4 — 6 were characterized by NMR, vibrational and MS spectra, as well as by X‐ray structure determinations. According to this, 4 forms centrosymmetrical and therefore planar Ga₂O₂ four‐membered rings. 5 and 6 possess basically the same structural motif, central M³⁺ ion ( 5 : In³⁺; 6 : Ga³⁺) coordinated by three metalate units ( 5 : [Me₂In(O^cHex)₂]^—; 6 : [MeGa(OCH₂Ph)₃]^—). The central M³⁺ ions have always coordination number (CN) six while the three surrounding metal ions possess CN 4. Because of the spectroscopic findings 6 must exist in two isomers (1:1). The C₃‐symmetrical isomer C₃‐ 6 was characterized by X‐ray analysis, while the isomer C₁‐ 6 could by described mainly by the complex NMR data.     

Synthesis of Bicyclic Compounds Derived from 1,2,4-Benzotriazines

The synthesis of bicyclic compounds derived from benzo[1,2,4]triazines is described.     

The Synthesis of 5,11,17-Trihalotetracyclo [13.3.1.13,7.19,13]henicosa-1 (19),3,5,7 (20),9,11,13 (21), 15,17-nonaene-19,20,21-triols and 5,11,17-trihalo-19,20,21-trihydroxytetracyclo [13.3.1.13,7. 19,13]henicosa-1 (19),3,5,7 (20),9,11,13(21), 15,17-nonaene-8,14-dione [1]. Cyclo-derivatives of Phloroglucide Analogues

The synthesis of the title compounds ( 1 and 3 ) is described. Some of the compounds prepared were found to be active against a number of pathogenic microorganisms in vitro. Structure-activity relationship is briefly discussed.     

Simultaneous Voltammetric Determination of Lead and Tin by Adsorptive Differential Pulse Stripping Method and Orthogonal Signal Correction‐Partial Least Squares in Water Samples

An adsorptive differential pulse stripping method for the simultaneous determination of lead and tin is proposed. The procedure involves an adsorptive accumulation of lead and tin on a hanging mercury drop electrode (HMDE), followed by oxidation of adsorbed lead and tin by voltammetric scan using differential pulse modulation. The optimum experimental conditions are: 0.2 mol L^?1 HNO₃, accumulation potential of ?900 mV versus Ag/AgCl, accumulation time of 200 s, scan rate of 20 mV s^?1 and pulse height of 80 mV. Lead and tin peak currents were observed in the same potential region at about ?400 mV. The simultaneous determination of lead and tin by using voltammetry is a difficult problem in analytical chemistry, due to voltammogram interferences. The resolution of a mixture of lead and tin by the application of orthogonal signal correction‐partial least squares (OSC‐PLS) was performed. The linear dynamic ranges were 0.003‐0.35 and 0.008‐0.50 μg mL^?1 and detection limits were land 3 ng mL^?1 for lead and tin, respectively. The RMSEP for lead and tin with OSC and without OSC were 2.8737, 6.0557 and 8.0941, 9.5151, respectively. The capability of the method for the analysis of real samples was evaluated by the determination of lead and tin in water samples with satisfactory results.     

Reaktionen von tBuPLi2 mit Carbodiimiden

Reaction of ^tBuPLi₂ with Carbodiimides The reaction of bis(cyclohexyl)carbodiimide with ^tBuPLi₂ in THF at 20 °C leads to the tetranuclear Li‐complex [Li₄(THF)₂{^tBuP([^cHexN]₂C)₂}₂] ( 1 ). No addition on the carbodiimide but a silyl transfer was observed under similar conditions during the treatment of bis(trimethylsilyl)carbodiimide with ^tBuPLi₂ to give the lithium salts ^tBuP(SiMe₃)Li and [Li(THF)(Me₃SiN‐C≡N)]_n ( 2 ). 1 was characterized by NMR, IR and RE spectroscopy, mass spectrometry and X‐ray analyses. Theoretical calculations were performed for 1 . According to the structural investigations 1 consists ofa central centrosymmetrical twelve‐membered Li₂N₄C₄P₂ ring adjacent by two six‐membered LiN₂C₂P rings. The peripheric Li⁺ cations posssess coordination number (cn) 3 buildt‐up by two N atoms and a THF ligand, while the two central Li⁺ cations possess only cn 2. However, the theoretical calculations have shown no relevant bonding Li···Li or Li···P interaction.     

An approach to estimate the energy and strength of the intramolecular hydrogen bond in different conformers of 4‐methylamino‐3‐penten‐2‐one

The molecular structure and intramolecular hydrogen bond energy of 32 conformers of 4‐methylamino‐3‐penten‐2‐one were investigated at MP2 and B3LYP levels of theory using the standard 6–31G** basis set and AIM analyses. Furthermore, calculations for all the possible conformations of 4‐methylamino‐3‐penten‐2‐one in water solution were also carried out at B3LYP/6–31G** level of theory. The calculated geometrical parameters and conformational analyses in gas phase and water solution show that the ketoamine conformers of this compound are more stable than the other conformers (i.e., enolimine and ketoimine). This stability is mainly due to the formation of a strong N? H···O intramolecular hydrogen bond, which is assisted by π‐electrons resonance. Hydrogen bond energies for all conformers of 4‐methylamino‐3‐penten‐2‐one were obtained from the related rotamers method. The nature of intramolecular hydrogen bond existing within 4‐methylamino‐3‐penten‐2‐one has been investigated by means of the Bader theory of atoms in molecules, which is based on topological properties of the electron density. The results of these calculations support the results which obtained by related rotamers method. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Synthesis,Characterization and Crystal Structures of new Coordination Polymers of Cerium(III) and Samarium(III) Containing 2,6‐Pyridinedicarboxylic Acid

The reaction of 2,6‐pyridinedicarboxylic acid ( 1 , LH₂) with CeCl₃·7H₂O and Sm(NO₃)₃·6H₂O in the presence of triethylamine led to the coordination polymer complexes [M(L)(LH)(H₂O)₂]·4H₂O [M = Ce ( 2 ) and Sm ( 3 )]. Both complexes were characterized by elemental analyses, IR spectroscopy and the crystal structures of 2 and 3 . Crystal data for 2 at ?80 °C: monoclinic, space group P2₁/c, a = 1404.6(1), b = 1122.1(1), c = 1296.1(1) pm, β = 102.09(1)°, Z = 4, R₁ = 0.0217 and for 3 at ?80 °C: monoclinic, space group P2₁/c, a = 1395.1(1), b = 1120.1(1), c = 1282.8(1) pm, β = 102.71(1)°, Z = 4, R₁ = 0.019.     

Diorganomorpholinometallane von Gallium und Indium – Monomer‐Dimer‐Gleichgewichte in Lösung

Diorganomorpholinometalates of Gallium and Indium – Monomer‐Dimer‐Equilibrium in Solution The reaction of Li[N(CH₂CH₂)₂O] (LiMorpholinate; Li(Morph)) with Me₂GaCl and Me₂InCl gives by salt‐elimination the diorganoamidometalates Me₂M(Morph) ( M = Ga: 1 ; M = In: 2 ), respectively. 1 and 2 were characterized by NMR and vibrational spectroscopy as well as by X‐ray structure determinations. According to this, centrosymmetrical dimers are present in the solid state while a monomer‐dimer equilibrium was assumed for the THF‐solution. Cryoscopic molecular weight determinations confirmed our assumptions.     

Traffic noise reduction due to the screening effect of balconies on a building façade

In this paper we discuss the use of self-protecting buildings as a means of reducing traffic noise nuisance. The results obtained from a computer model of one self-protecting configuration, namely a closed balcony shielding a window into a room, are compared with measurements made on a 1:10 scale model of this situation. From a comparison of these results an empirical equation is given which permits the benefits of a closed balcony to be predicted from the application of standard noise screen formulae.Since the degree of annoyance experienced by people exposed to traffic noise has been shown to be influenced by temporal variations of level, the computer model was extended to enable the effect of the balcony on this variability to be assessed.