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81.
Elemental I(2) and Br(2) cleanly react with the 3:3 Pt(ii) metallamacrocycle of 3,3,3',3'-tetra(n-butyl)-1,1'-terephthaloylbis(thiourea)(cis-[Pt(II)(3)(L(p)(1)-S,O)(3)]3), in chloroform at room temperature, to yield oxidative addition products; (195)Pt NMR studies reveal that a stepwise oxidative addition readily occurs to each of the Pt(ii) centres in the metallamacrocycle to yield the mixed valence species cis-[Pt(II)(2)Pt(IV)I(2)(L(p)(1)-S,O)(3)] and cis-[Pt(II)Pt(IV)(2)I(4)(L(p)(1)-S,O)(3)], and the fully oxidised cis-[Pt(IV)(3)I(6)(L(p)(1)-S,O)(3)] in solution, depending on the mole ratio I(2):3. Similar results are obtained on treatment of solutions of 3 with elemental Br(2). Treatment of the corresponding 2:2 Pt(ii) complex of 3,3,3',3'-tetraethyl-1,1'-isophthaloylbis(thiourea)(cis-[Pt(II)(2)(L(m)(1)-S,O)(2)]4) with iodine, results in facile oxidative addition to yield cis-[Pt(IV)(2)(L(m)(1)-S,O)(2)I(4)], with a trans-Pt(iv)-iodo arrangement. Molecules in the crystal structure of 5 have their trans-Pt(iv)-iodo axes essentially aligned, with very close intermolecular iodide contacts (3.775(1)A), resulting in chains of weakly bound metallamacrocycles in the solid. An alternative electrolytic synthesis method, using a simple two-compartment glass cell containing 4 and a chosen halide salt in dichloromethane, led to the formation of cis-[Pt(IV)(2)(L(m)(1)-S,O)(2)Br(4)] 6 and cis-[Pt(IV)(2)(L(m)(1)-S,O)(2)Cl(4)] 7, completing characterization of a series of first-reported trans-Pt(iv)-X (X=I, Br, Cl) metallamacrocyclic complexes. 相似文献
82.
Neuvonen H Neuvonen K Koch A Kleinpeter E 《The journal of physical chemistry. A》2005,109(28):6279-6289
Equilibria between the Z (tau1= 0 degrees) and E (tau1= 180 degrees) conformers of p-substituted phenyl acetates 4 and trifluoroacetates 5 (X = OMe, Me, H, Cl, CN, NO2) were studied by ab initio calculations at the HF/6-31G* and MP2/6-31G* levels of theory. The preference for the Z conformer, DeltaE(HF), was calculated to be 5.36 kcal mol(-1) and 7.50 kcal mol(-1) for phenyl acetate and phenyl trifluoroacetate (i.e., with X = H), respectively. The increasing electron-withdrawing ability of the phenyl substituent X increases the preference of the Z conformer. An excellent correlation with a negative slope was observed for both series between DeltaE of the E-Z equilibrium and the Hammett sigma constant. By using an appropriate isodesmic reaction, it was shown that electron-withdrawing substituents decrease the stability of both conformers, but the effect is higher with the E conformer. Electron-withdrawing phenyl substituents decrease the delocalization of the lone pair of the ether oxygen to the C=O antibonding orbital (nO--> pi*C=O) in both the E and Z forms and in both series studied; this effect is higher in the E conformer than in the Z conformer. The nO --> pi*C=O electron donation has a minimum value with tau1= 90 degrees and a maximum value with tau1= 0 degrees (the Z conformer), the value with tau1= 180 degrees (the E conformer) being between these two values, obviously due to steric hindrance. The effects of the phenyl substituents on the reactivity of the esters studied are discussed in terms of molecular orbital interactions. ED/EW substituents adjust the availability of the pi*C=O antibonding orbital to interact with the lone pair orbital of the attacking nucleophile and therefore affect the reactivity: EW substituents increase and ED substituents decrease it. Excellent correlations were observed between the rate coefficients of nucleophilic acyl substitutions and pi*C=O occupancies of the ester series 4 and 5. 相似文献
83.
Patrick Koch Carl Djerassi Vijai Lakshmi Francis J. Schmitz 《Helvetica chimica acta》1983,66(8):2431-2436
Thirty-two sterols are identified in the sponge Hyrtios sp. In addition to fourteen monohydroxylated compounds, the sterol fraction contains eight functionalized sidechain sterols, three of them new: 3 β-hydroxy-24-norchol-5-en-23-al (19) , (22-trans)-3 β-hydroxycholest-5, 22-dien-24-one (20) and (22R, 23R, 24S) or (22S, 23S, 24S)- 22,23-epoxy-24-methylchoest-5-en-3 β-ol (24). The probable biological origin, rather than artifact production, of these undescribed components is discussed. 相似文献
84.
Differential thermal analysis (DTA) is an effective means for studying chemical reactions, but its application to reaction kinetics is handicapped by the involvement of temperature feedback from the reaction heat and by the solvent dependence of the thermal conductivity.General, empirical relationships are derived from digital computer application which allow to transform half width and shape index of a DTA curve of any first-order process in a uniformly temperated sample to the values of the corresponding rate curve at linearly increased temperature.The expressions are complemented by some new relationships for an n-order reaction and are useful for the kinetic study of complex processes. 相似文献
85.
Matthias HeydenreichAndreas Koch László LázárIstván Szatmári Reijo SillanpääErich Kleinpeter Ferenc Fülöp 《Tetrahedron》2003,59(11):1951-1959
Starting from the 1′- or 2′-phenyl-substituted 1-(2′-hydroxyethyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline diastereomers 3 and 6, 4-unsubstituted and 4-(p-nitrophenyl)- and 4-oxo-substituted 1-phenyl- and 2-phenyl-9,10-dimethoxy-2H,4H-1,6,7,11b-tetrahydro-1,3-oxazino[4,3-a]isoquinolines (7-12) were prepared. The relative configurations and the predominant conformations of the products were determined by NMR spectroscopy, by quantum chemical calculations and, for (2R∗,4S∗,11bR∗)-9,10-dimethoxy-4-(p-nitrophenyl)-2-phenyl-2H,4H-1,6,7,11b-tetrahydro-1,3-oxazino[4,3-a]isoquinoline (11), by X-ray diffraction. 相似文献
86.
K. H. Koch und K. Ohls 《Fresenius' Journal of Analytical Chemistry》1969,247(3-4):239-243
Zusammenfassung Ein neues lösungsspektrographisches Zerstäubungsverfahren wird beschrieben, bei dem die Lösung so zerstäubt wird, daß sie die Graphitelektroden nicht berührt. Mit diesem Verfahren könnten 10–3 bis 10–5 % Al, B, Cr, Cu, Mg, Mn, Mo, Ni, Si, Sn, Ti, V und Zr in Eisen und Stahl bestimmt werden.Zur Bestimmung von Verunreinigungen oder Einschlüssen in Stahl wird ein spektrographisches Verfahren mit Preßlingselektroden empfohlen, das nur 0,1–1 mg Rückstand benötigt. Oxide von Al, B, Ca, Co, Cu, Cr, Fe, Mg, Mn, Mo, Nb, Ni, Pb, Si, Sn, Sr, Ti, V, Zn und Zr konnten bis herab zu etwa 10–7 g erfaßt werden.
Methods for the determination of trace elements from metallic samples
The principles of a new spectrographical atomizing-method of solution are described. The solution has to be atomized into a gap without contacting the surface of the graphite electrodes. In this way the exact determination of 10–3 to 10–5 % of Al, B, Cr, Cu, Mg, Mn, Mo, Ni, Si, Sn, Ti, V and Zr in iron and steel is possible.The microanalytical determination of impurities or inclusions in steel has been achieved by a spectrographical method with briquette electrodes. The necessary amount of isolation residue is only 0.1–1 mg. The oxides of Al, B, Ca, Co, Cu, Cr, Fe, Mg, Mn, Mo, Nb, Ni, Pb, Si, Sn, Sr, Ti, V, Zn and Zr can be accurately determined by this procedure. The limit of determination is about 10–7 g.相似文献
87.
O. G. Koch 《Fresenius' Journal of Analytical Chemistry》1977,286(1-2):14-19
Zusammenfassung Es wird eine automatisierte Apparatur zur schnellen, massenspektrometrischen Bestimmung von Sauerstoff und Stickstoff in Stahl beschrieben. Die Stahlprobe wird unter Argon im Gleichstrombogen geschmolzen und die extrahierten Gase Kohlenmonoxid und Stickstoff werden massenspektrometrisch bestimmt. Die relative Standardabweichung beträgt ±3–5% für Sauerstoff und ±3–8% für Stickstoff. Die Nachweisgrenzen liegen bei 10 pp106 O2 und 3 pp106 N2. Der Zeitbedarf für eine Analyse beträgt 85 s.Herrn H. Siffrin danke ich für die sorgfältige Durchführung der zahlreichen Versuche. 相似文献
88.
The optical constants in the photon energy range between 4 and 10.5 eV for E ?b on (001) and E ?L and E ⊥ L on the (010) plane are discussed. In particular the influence of macroscopic fields on the optical properties of anisotropic crystals is considered. For E ? a on the (001) plane reflection spectra have been measured at various angles of incidence. These data and results obtained recently by Hymowitz and Clark for several artificially prepared crystal faces are discussed on the basis of the frequency dependend dielectric functions. New information on the directional dispersion of exciton bands is thus obtained. 相似文献
89.
Yi SS Reichert EL Holthausen MC Koch W Weisshaar JC 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(12):2232-2245
A pulsed beam of Co+(3F4) crosses a pulsed beam of C3H8 or C3D8 gas under single collision conditions at collision energies of 0.01 eV and 0.21 eV. After a variable time delay t(ext) = 1-8 micros a fast high voltage pulse extracts product ions into a field-free flight tube for mass analysis. Consistent with earlier work, we observe prompt CoC3H6+ +H2 elimination products in 3:1 excess over CoC2H4+ +CH4 products at 0.21 eV on a 2-10 micros time scale. Long-lived CoC3H8+ complexes fragment predominantly back to Co+ +C3H8 reactants and to H2 elimination products on a 6-24 micros time scale. Density functional theory (B3LYP) calculations provide energies, geometries, and harmonic vibrational frequencies at key stationary points for use in a statistical rate model of the reaction. By adjusting two key multicenter transition state (MCTS) energies downward by 4-7 kcal mol(-1), we obtain good agreement with our decay time results and with the cross section versus collision energy of Armentrout and co-workers from 0.1-1.0 eV. B3LYP theory succeeds in finding relative energies of the MCTSs leading to CH4 and H2 in the proper order to explain the different product branching ratio for Co+ (which favors H2 over CH4) compared with its nearest neighbors Fe+ and Ni+ (which favor CH4 over H2). 相似文献
90.
G. Czerwenka R. Koch und E. Scheubeck 《Fresenius' Journal of Analytical Chemistry》1976,279(4):269-273
Zusammenfassung Die Anwendung einer chloridionensensitiven Elektrode für die direktpotentiometrische Chloridbestimmung in galvanischen BÄdern wird beschrieben und eine genaue Arbeitsvorschrift sowie drei verschiedene Auswerteverfahren angegeben. Die Messungen wurden in einem Bereich von 30–250 mg Cl– je Liter Badlösung an Modellösungen durchgeführt. Die einzelnen Methoden ergaben eine Standardabweichung von ±2,1 mg bei Verwendung einer Eichkurve, ±2,2 mg beim Standardzusatzverfahren und ±3,6 mg bei der Direktablesung auf einer logarithmisch geteilten Skala eines mV-Meters. Ebenso wurden Messungen an einer Reihe von Badproben durchgeführt.Für wertvolle Anregungen und Diskussionen danken wir Herrn Schwank, Siemens AG, Abt. Informationselektronik. 相似文献