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101.
Hughes RP Meyer MA Tawa MD Ward AJ Williamson A Rheingold AL Zakharov LN 《Inorganic chemistry》2004,43(2):747-756
Reaction of Pd(TMEDA)(CH(3))(2) [TMEDA = tetramethylethylenediamine] with fluoroalkyl iodides R(F)I affords a series of square planar Pd(II) complexes Pd(TMEDA)(CH(3))(R(F)) [R(F) = CF(2)CF(3) (9), CFHCF(3) (10), CH(2)CF(3) (11)], presumably by oxidative addition followed by reductive elimination of CH(3)I. The solid-state structures of each compound have been determined by single crystal X-ray diffraction studies, allowing the effect of increasing alpha-fluorination on the structural trans-influence of alkyl ligands to be examined. In these compounds there is no significant difference observed in the trans-influence of the three fluorinated alkyl ligands toward the trans-N atom, although a significant cis-influence on the neighboring methyl ligand is apparent. Oxidative addition of the same series of fluoroalkyl ligands to the corresponding Pt(TMEDA)(CH(3))(2) affords octahedral Pt(IV) complexes trans-Pt(TMEDA)(CH(3))(2)(R(F))I [R(F) = CF(2)CF(3) (12), CFHCF(3) (13), CH(2)CF(3) (14)] as the kinetic products. In each case, subsequent isomerization to the corresponding all cis-isomers is observed; in the case of 13, the stereocenter at the alpha-carbon results in two diastereomeric cis-isomers, which are formed at different rates. The molecular structures of 13 and its more stable all cis-isomer 16b have been crystallographically determined. Kinetic studies of the trans-cis isomerization reactions show the mechanism to involve a polar transition state, presumably involving iodide dissociation, followed by rearrangement of the cation, and iodide recombination. High dielectric solvents increase the rate, but solvent coordinating ability has no effect. Dissolved salts (LiI, LiOTf) show normal accelerative salt effects, with no inhibition in the case of added iodide, consistent with the formation of an intimate ion pair intermediate. The kinetic parameters show that the trans-effects of fluoroalkyl ligands in these compounds follow the order expected from the relative sigma-donor properties of the ligands, with CF(2)CF(3) < CFHCF(3) < CH(2)CF(3). 相似文献
102.
J. Hladký S. NĚmeček M. Novák A. Prokeš J. Votruba K. -F. Albrecht A. Meyer M. Sachwitz B. N. Guskov V. G. Krivokhizhin M. F. Likhachev I. A. Savin G. Vesztergombi 《Czechoslovak Journal of Physics》1977,27(11):1210-1218
Results of the first elastic K
S
o
regeneration experiment on carbon, using magnetic spark chamber spectrometer, are presented in the beam momentum interval 10p50 GeV/c. The d ifferentia cross section d/dt is reconstructed in the range 0·0025–t0·02 (GeV/c)2 and its slopeB is found to be momentum independent with an average valueB=(65±11) (GeV/c)–2. The results are in agreement with the calculations using the coherent production model. 相似文献
103.
M. W. Müller A. Merz M. -W. Ruf H. Hotop W. Meyer M. Movre 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1991,21(2):89-112
We have carried out a comprehensive experimental and theoretical investigation of the autoionizing collision systems He*(23 S, 21 S) + He*(23 S). We present high resolution electron energy spectra, obtained with a single He* beam (average relative collision energy 〈E rel〉=1.6 meV) and with crossed He* beams (〈E rel〉> =61 meV). The spectra show substantial structure, and under single beam conditions fast oscillations due to the interference of incoming and outgoing heavy particle waves in the entrance channels are observed. Accurate ab initio potential curves for the seven lowest He*—He*(Σ) molecular states have been obtained from a Feshbach projection scheme, and width functions for He*(23 S) + He*(23 S) have been derived by Stieltjes imaging. Based on these ab initio data, detailed quantum mechanical calculations of the electron spectra have been carried out and provide a thorough understanding of the experimentally observed spectral features. Good overall agreement of the calculated spectra with the experimental data is observed. The close coincidence in the positions of the experimental and theoretical peaks, especially for He*(23 S) + He*(23 S), underlines the reliability of the ab initio potentials. In the He*(21 S) + He*(23 S) electron spectrum, the dominant peak is traced to be due to autoionization from the 23Σ+ g molecular state accessed via an avoided crossing. We also present a detailed discussion of the total ionization cross sections σtot and of the fraction σAI/σtot for associative ionization together with a critical comparison with previous work. The ionization probabilities for close collisions in entrance channels, from which autoionization is spin-allowed, are near unity, and therefore the absolute values and the collision energy dependence of the total cross sections simply reflect the long-range behaviour of the excited state potentials. 相似文献
104.
La2O(CN2)2 was synthesized from a 1:1:2 molar reaction mixture of LaCl3, LaOCl, and Li2(CN2) at 650 °C. Well developed single crystals were grown from a LiCl‐KCl flux. The crystal structure was refined as monoclinic (space group C2/c, Z = 2, a = 13.530(2) Å, b = 6.250(1) Å, c = 6.1017(9) Å, β = 104.81(2)°) from single crystal X‐ray diffraction data. The La3+ and (CN2)2— ions in the crystal structure of La2O(CN2)2 can be compared to Fe3+ and S22— ions in the cubic pyrite structure, being arranged like in a distorted NaCl type structure with their centers of gravity. In addition, the O2— ions in La2O(CN2)2 are occupying 1/4 of the tetrahedral voids formed by the arrangement of metal ions. 相似文献
105.
Ternary Rare-Earth Halides of the A2MX5 Type (A = K, In, NH4, Rb, Cs; X = Cl, Br, I) Ternary rare-earth (=M) chlorides, bromides, and iodides In2MCl5, (NH4)2MCl5, Rb2MCl5, Cs2MCl5, CsRbMCl5, K2MBr5, Rb2MBr5, K2MI5, and Rb2MI5 have been synthesized. Single crystals of In2PrCl5, Rb2PrCl5, K2PrBr5, and K2PrI5 were grown and the structures refined. The other halides were characterized by x-ray powder patterns. They are isotypic either with K2PrCl5(orthorhombic, Pnma, Z = 4, hexagonal arrangement of chains of edge-connected polyhedra [PrX7]) or with Cs2DyCl5 (orthorhombic, Pbnm, Z = 4, hexagonal arrangement of cis-corner-connected octahedra [DyCl6]) which may be discriminated in structure field diagrams. The thermal expansion was investigated für Cs2LuCl5 and Rb2PrX5 (X = Cl, Br, I). 相似文献
106.
J. Meyer 《Fresenius' Journal of Analytical Chemistry》1967,231(4):241-252
Zusammenfassung Es wird ein Verfahren zur Spurenbestimmung in Reinstsilber und Reinstsilberverbindungen beschrieben, das besonders für Routineanalysen geeignet ist. Das Verfahren beruht auf der hochselektiven Abtrennung des Matrixelementes von sämtlichen elektropositiveren Begleitspuren durch Reduktion mit Ameisensäure aus salpetersaurer Lösung, wobei das Silber als Amalgam abgeschieden wird. In der Spurenanreicherungslösung werden die für die Reinheitskontrolle von Silber und dessen Verbindungen wichtigsten Begleitelemente Pb, Cu, Cd, Zn amalgamvoltammetrisch, Tl, Ga, In, Fe, Ni, Mn flammenspektrometrisch und As photometrisch bestimmt. Die relativen Standardabweichungen liegen zwischen 2 und 13%, die Nachweisgrenzen zwischen 10–6 und 10–5%. Die prinzipiellen Möglichkeiten der Bestimmung weiterer Elemente sowie der Anwendung anderer Bestimmungsmethoden werden erörtert.über bisher bekannte Verfahren zur Spurenbestimmung in Silber wird berichtet.
Summary A method for the determination of trace amounts of metallic impurities in high-purity silver and silver salts is described. The procedure is based on an extremely selective separation of the silver matrix from all accompanying trace elements more electropositive than silver. The silver is separated by reducing a nitric acid solution of the sample with formic acid and depositing the silver as an amalgam. In the solution containing the enriched traces the elements being most important for the purity control of silver and its salts are detected voltammetrically (Pb, Cu, Cd, Zn), flame-spectrometrically (Tl, Ga, In, Fe, Ni, Mn) and photometrically (As). The relative standard deviations for the different elements were found to be between 0.02 and 0.13, the limits of detection between 10–6 and 10–5%. The possibilities to detect further elements and to apply other determination methods are pointed out.Previously known procedures for detecting trace amounts of impurities in silver are reported.相似文献
107.
108.
The reactions between trans-[Os(IV)(tpy)(Cl)(2)(NCN)] (1) and PPh(3) and between trans-[Os(IV)(tpy)(Cl)(2)(NPPh(3))](+) (2) and CN(-) provide new examples of double derivatization of the nitrido ligand in an Os(VI)-nitrido complex (Os(VI)N). The nitrilic N-bound product from the first reaction, trans-[Os(II)(tpy)(Cl)(2)(NCNPPh(3))] (3), is the coordination isomer of the first iminic N-bound product from the second reaction, trans-[Os(II)(tpy)(Cl)(2)(N(CN)(PPh(3)))] (4). In CH(3)CN at 45 degrees C, 4 undergoes isomerrization to 3 followed by solvolysis and release of (N-cyano)iminophosphorane, NCNPPh(3). These reactions demonstrate new double derivatization reactions of the nitrido ligand in Os(VI)N with its implied synthetic utility. 相似文献
109.
Gerd Meyer 《无机化学与普通化学杂志》1981,478(7):39-51
Indium Sesquichloride, In2Cl3: a Pseudobinary, Mixed-valence Indium(I) Hexachloroindate(III) Colorless In2Cl3, obtained by reduction of InCl3 with metallic In, according to In[InIIICl6] a pseudobinary, mixed-valence indium(I) hexachloroindate(III), crystallizes orthorhombic (Pnma, Z = 32) with a = 1261.4(3), b = 2523.8(5), c = 1456.2(2) pm (Guinier-Simon data), Vm(In2Cl3) = 87.3 cm3 × mol?1. InIII occupies octahedral holes separated from each other (d?(InIII? Cl) = 251 pm). Coordination numbers of 7 to 11 are observed for InI (d?(InI? Cl) = 329–359 pm). In2Cl3 is isotypic with α-Tl2Cl3. 相似文献
110.
Victor E. Meyer 《Journal of polymer science. Part A, Polymer chemistry》1967,5(6):1289-1296
From the conversion–composition data of Gruber and Elias, the reactivity ratios of styrene (M1) and methyl methacrylate (M2) were calculated to be r1 = 0.55 ± 0.02 and r2 = 0.58 ± 0.06 at 90°C. The least-squares method was then used on these and literature values at other temperatures to obtain the Arrhenius expressions: In r1 = 0.04736 – (235.45/T), and ln r2 = 0.1183 – (285.36/T). Using literature values for the homopolymerization steps, A11 = 2.2 × 107l./mole-sec., E11 = 7.8 kcal./mole, and A22 = 0.51 × 107 l./mole-sec.?1, E22 = 6.3 kcal./mole, activation energies and frequency factors were then calculated for the cross-polymerization steps: A12 = 2.1 × 107 l./mole-sec., E12 = 7.3 kcal./mole, and A21 = 0.45 × 107 l./mole-sec., E21 = 5.7 kcal./mole. 相似文献