Darstellung von Acetatoblei(IV)- und Acetatozinn(IV)- manganpentacarbonylen durch Acidolyse von (C6H5)4–n−M[Mn(CO)5]n (M  Sn,Pb; n = 1, 2) mit Essigsäure

Preparation of Acetatolead(1V) and Acetatotin(1V) Manganese Pentacarbonyls by Acidolysis of (C₆H₅)_4?n M[Mn(CO)₅]_n (M ? Sn, Pb; n = 1, 2) with Acetic Acid By acidolysis of (C₆H₅)_4?nM[Mn(CO)₅]_n (M ? Sn, Pb; n = 1, 2) with acetic acid no M? Mn bonds are broken, but M? C bonds. In this reaction (CH₃COO)₂M[Mn(CO)₅]₂ is formed from (C₆H₅)₂M[Mn(CO)₅]₂, and (CH₃COO)₃SnMn(CO)₅ and (CH₃COO)₂C₆H₅PbMn(CO)₅ from (C₆H₅)₃MMn-(CO)₅. (CH₃COO)₂C₆H₅SnMn(CO)₅ is prepared from Cl₂C₆H₅SnMn(CO)₅ and AgCH₃COO. According to IR spectroscopic data the acetato ligands of the diacetato complexes are bidentate, while in (CH₃COO)₃SnMn(CO)₅ bi- and monodentate carboxylate groups are present. For the central atoms Sn and Pb octahedral coordination is proposed.     

On the magnetic properties and the phase composition of the Cr2O3?MnOx-system (2 ≥ x ≥ 1.5)

The mixed oxide system Cr₂O₃? MnO_x (2 ≥ x ≥ 1.5) was investigated by X-ray diffraction, by measurements of magnetic susceptibility, and by chemical determination of excess oxygen (BUNSEN'S method). The Presence of the antiferromagnetic oxides Cr₂O₃, β-MnO₂, α-Mn₂O₃ and a ferromagnetic phase Cr_1?yMn_yO₂ was stated. The formation of the latter with fourvalent chromium is explained by a lattice induction effect of the MnO₂ (rutile type).     

Preliminary estimate of the cost of ethanol production for ssf technology

The Solar Energy Research Institute (SERI) recently completed a detailed engineering and economic analysis of the simultaneous saccharification and fermentation (SSF) based wood-to-ethanol process. The reference-case design was based on a plant capacity of 1920 dry t/d and a wood cost of $42/dry t. For this case, the preliminary estimate of the production cost of the ethanol product is about $1.22/gal. The combined effects of optimizing SSF enzyme loading, increasing plant capacity to 10,000 dry t/d, and reducing wood cost to $34/dry t are to reduce the preliminary estimate of the production cost to about $0.95/gal. Other technological improvements may further reduce the production cost. Certain technical assumptions, inherent in the analysis, are being investigated further.

     

Syntheses of bile pigments. Part 15. First unequivocal assignment of the absolute configuration of an urobilinoid bile pigment by X-ray diffraction analysis of its synthetic precursor

(?)-(4S,16S)-8, 12-bis[de(2-carboxyethyl)]mesourobilin-IIIα hydrochloride ( 8 ) has been synthesized from the enantiomerically pure 1,4,5,10-tetrahydro-1-oxodipyrrin-9-carboxylic-acid precursor 6a whose absolute configuration was determined by X-ray diffraction analysis of the N-[(S)-1-(1-naphthyl)ethyl] carboxamide 7b . The present results prove unequivocally that an (S,S)-configurated urobilin chromophore displays a negative Cotton effect in the VIS absorption range. However, the helicity of the inherently dissymmetric chromophore remains undetermined.     

Optically detected magnetic resonance study of the lowest excited triplet state of aromatic thioketones: Xanthione

The aromatic thioketone xanthione has been investigated by means of the optically detected magnetic resonance (ODMR) technique in a n-hexane matrix at ≈ 1.1 K. It was established that the short-lived red emission, which is characteristic for many thione molecules, is phosphorescence. At high temperatures (77 K) this phosphorescence originates mainly (>80%) from the T₁^z (n, π*) sublevel (k_z^(r) >k_x^(r), k_y^(r). At low temperature (1.1 K) the intersystem crossing following S₂ (π, π*) ← S₀ excitation is a highly spin-sublevel selective process which populates predominantly the T₁^x and T₁^y, levels. Hence, the slow spin—lattice relaxation phosphorescence at low temperature originates from these sublevels. A value of 0.0611 cm^?1 was obtained for the zero-field parameter |E|/hc. A lower limit of 0.66 cm^?1 has been found for the zero-field parameter |D|/hc. This value is considerably larger than those observed for ketones, and it is shown that spin—orbit coupling contributes strongly to the zero-field splitting.     

Beitrag zur Kenntnis des Systems Vanadin—Chrom—Stickstoff

The System V–Cr–N has been investigated at 1100 and 1400 °C and at nitrogen pressures between 1 and 1000 atmospheres by X-ray techniques. VN and CrN on the one hand and V₂N and Cr₂N on the other are forming complete series of solid solutions. The phase field of the mononitride solid solution is dependent on nitrogen pressure and temperature conditions.

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Auszug aus der Diplomarbeit des Herrn Dipl.-Ing. Dr.W. Schebesta.     

Traceless solid-phase synthesis of 2,4,6-chlorodiamino and triaminopyrimidines

An effective traceless solid-phase synthesis of chloro-diaminopyrimidines via an amino-de-chlorination reaction of polymer-bound 4-alkoxycarbonylamino-2,6-dichloropyrimidines has been developed. After release from the polymer the target molecules were obtained in good to excellent purity, although with modest regiocontrol. Further reaction of solid-supported N-alkoxycarbonyl-chloro-diaminopyrimidines with secondary amines afforded triaminopyrimidines in good purity under mild conditions, whereas less nucleophilic primary amines did not perform well under the conditions explored so far.     

Amperometry of thiols in a flow-injection system with a nickel oxide electrode

The electrochemical oxidation of a series of thils on the surface of a nickel oxide electrode is investigated in a flow-injection system. The background electrolyte is 0.1 M NaOH containing 5 × 10^?65 M NiSO₄ and the injected sample volume is 25 μl. The net peak current is observed at +0.46 V vs. SCE for thiols dissolved in pH 3.0 phthalate buffer. The upper limit of linearity extends to 10^?3 M. The relative standard deviation for ten replicate measurements on 10^?4 M ethanethiol is 1.6%. The lower limits of detection are between 3 × 10^?5 and 2 × 10^?4 M for a series of thiols. Peak shapes indicate that thiolate oxidation mediated by a higher oxide layer on the electrode rather than mass transport or adsorption / rearrangement is the rate-determining step.     

PHYTOCHROME-MEDIATED GERMINATION: EFFECTS OF BRIEF HIGH TEMPERATURE TREATMENTS

Abstract— Brief high temperature treatments, applied early in the pregerminative period to radiation-requiring seeds of lettuce, inhibited both dark and radiation-induced germination. The inhibition increased with increasing incubation temperature. There was little difference in the germination percentage whether the inductive irradiation was applied before or after the high temperature treatment. When the high temperature treatment preceded induction, there was an increase in the radiation dosage required for maximum germination. These findings are interpreted in terms of lability of physiologically active phytochrome to higher temperatures.     

Darstellung und Reaktionen des 3-Ethinyl-2,4-diformyl-pentandials

Preparation and physical and chemical properties of 3-ethinyl-2,4-diformyl-pentandial (3 a) and its salts are described.3 a contains 2 malonaldehyde groups. Starting from3 a, 4H-pyranes, 4H-dihydropyridines, dipyrazoles, diisoxazoles, bisdiazepines and vinamidine derivates are obtained.

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