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991.
CrIII Phthalocyaninates: Synthesis, Properties, and Crystal Structure of l-Bis(triphenylphosphine)iminium trans-Di(nitrito(O))phthalocyaninato(2–)chromate(III) [Cr(H2O)2Pc2?]Ix reacts with excess (PNP)NO2 in dimethylformamide to yield less soluble greenblack l-bis(triphenylphosphine)iminium trans-di(nitrito(O))phthalocyaninato(2–)chromate(III), l(PNP)trans[Cr(ONO)2Pc2?], which crystallizes in the triclinic space group P1 (No. 2) with Z = 2. The Cr atom is in the center of the Pc2? ligand and the two nitrite ions are monodentate O-coordinated in a mutually trans arrangement to the Cr atom. The Cr? O and Cr? Niso bond distances are 1.9898(14) und 1.981(2) Å, respectively. The geometric data of the coordinated nitrite ion are: d(N? O) = 1.307(2) Å; d(N? O) = 1.205(2) Å; ?(O? N? O) = 113.7(2)°; ?(Cr? O? N) = 116.85(12)°. The non-bonding O atoms are trans to the Cr atom. The Pc2? ligand is slightly saddled. Three weak spin-allowed trip-quartet(TQ) transitions (in 103 cm?1): TQ1 (8.20) < TQ2 (11.3) < TQ3 (20.33) and the characteristic π-π* transitions of the Pc2? ligand: B (14.68) < Q1 (27.1) < Q2 (29.0) < N (35.4) are observed in the UV-VIS-NIR spectrum. Prominent luminescence spectra are obtained by excitation within the TQ1 region, in which the spin-forbidden trip-sextet transition at 7376 cm?1 dominates at low temperatures (T < 50 K). The vibrational spectra are discussed. In coincidence of the excitation lines with TQ3, vs(Cr? O) at 378 cm?1 is selectively resonance Raman (RR) enhanced. vas(Cr? O) is observed in the FIR spectrum at 391 cm?1. The following internal vibrations (in cm?1) of the nitrito ligand are in the MIR spectrum: vas(N? O)/1447 > vas(N? O)/1018/1029 > δ(O? N? O)/828 and in the RR-spectrum: vs(N? O)/1410 > vs(N? O)/952, the last followed by three overtones. 相似文献
992.
Summary Protein structure analysis is an indispensible tool in modern biological research. However, the isolation of a protein or the separation of peptides in a form suitable for sequence analysis is a considerable technical challenge. The two predominant separation methods in protein biochemistry are chromatography and electrophoresis. In this paper the position, advantaged and disadvantages of both HPLC and electrophoresis for the separation of amino acids, peptides and proteins in protein structure analysis are discussed. 相似文献
993.
Francesco S. Gentile Alexander Platonenko Khaled E. El-Kelany Michel Rérat Philippe D'Arco Roberto Dovesi 《Journal of computational chemistry》2020,41(17):1638-1644
The infrared (IR) and Raman spectra of eight substitutional carbon defects in silicon are computed at the quantum mechanical level by using a periodic supercell approach based on hybrid functionals, an all electron Gaussian type basis set and the CRYSTAL code. The single substitutional C s case and its combination with a vacancy (C sV and C sSiV) are considered first. The progressive saturation of the four bonds of a Si atom with C is then examined. The last set of defects consists of a chain of adjacent carbon atoms C, with i = 1–3. The simple substitutional case, C s, is the common first member of the three sets. All these defects show important, very characteristic features in their IR spectrum. One or two C related peaks dominate the spectra: at 596 cm−1 for C s (and C sSiV, the second neighbor vacancy is not shifting the C s peak), at 705 and 716 cm−1 for C sV, at 537 cm−1 for C and C (with additional peaks at 522, 655 and 689 for the latter only), at 607 and 624 cm−1, 601 and 643 cm−1, and 629 cm−1 for SiC, SiC, and SiC, respectively. Comparison with experiment allows to attribute many observed peaks to one of the C substitutional defects. Observed peaks above 720 cm−1 must be attributed to interstitial C or more complicated defects. 相似文献
994.
E. T. Denisov 《Russian Chemical Bulletin》2005,54(4):914-923
Interatomic distances in the reaction centers of the addition reactions of (i) H· to the C=C, C=O, N≡C, and C≡C bonds, (ii) ·CH3 radical to the C=C, C=O, and C≡C bonds, and (iii) alkyl, aminyl, and alkoxyl radicals to olefin C=C bonds were determined
using a new semiempirical method for calculating transition-state geometries of radical reactions. For all reactions of the
type X· + Y=Z → X— Y—Z· the r
#
X...Y distance in the transition state is a linear function of the enthalpy of reaction. Parameters of this dependence were determined
for seventeen classes of radical addition reactions. The bond elongation, Δr
#
X...Y, in the transition state decreases as the triplet repulsion, electronegativity difference between the atoms X and Y in the
reaction center, and the force constant of the attacked multiple bond increase.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 894–902, April, 2005. 相似文献
995.
Mikhail I. Kodess Marina A. Ezhikova Galina L. Levit Victor P. Krasnov Valery N. Charushin 《Journal of organometallic chemistry》2005,690(11):2766-2768
Experimental conditions for determination of enantiomeric composition of 1-substituted 3-aminocarboranes by 1H and 13C NMR spectroscopy using chiral shift reagent Eu(hfc)3 have been found. 相似文献
996.
Aziz Ghoufi Pierre Archirel Jean-Pierre Morel Nicole Morel-Desrosiers Anne Boutin Patrice Malfreyt 《Chemphyschem》2007,8(11):1648-1656
We report potential of mean force (PMF) calculations on the interaction between the p-sulfonatocalix[4]arene and a monovalent cation (Cs(+)). It has been recently shown from microcalorimetry and (133)Cs NMR experiments that the association with Cs(+) is governed by favourable cation-pi interactions and is characterized by the insertion of the cation into the cavity of the macrocycle. We show that the PMF calculation based upon a classical model is not able to reproduce both the thermodynamic properties of association and the insertion of the cation. In order to take into account the different contributions of the cation-pi interactions, we develop a new methodology consisting of changing the standard PMF by an additional contribution resulting from quantum calculations. The calculated thermodynamic properties of association are thus in line with the microcalorimetry and (133)Cs NMR experiments and the structure of the complex at the Gibbs free-energy minimum shows the insertion of the cation into the cavity of the calixarene. 相似文献
997.
Marijan Kočevar Branko Stanovnik Miha Tišler 《Monatshefte für Chemie / Chemical Monthly》1988,119(5):597-603
Pyrido[2,3:3,4]pyrazolo[5,1-c][1,2,4]benzotriazin-4(1H)ones were transformed via their oximes in aSemmler-Wolff aromatization process in the tetracyclic heteroaromatic amines4 or bySchmidt reaction into a mixture of the same amine4 and a ring enlarged lactam3. Syntheses of some halo pyrazolo[3,4-b]pyridines and a photochemical transformation of 3-azidopyrazolo[3,4-b]pyridine are also described.
Über dieSemmler-Wolff- undSchmidt-Reaktion einiger Pyrido[2,3:3,4]pyrazolo[5,1-c][1,2,4]benzotriazine
Zusammenfassung Pyrido[23:3,4]pyrazolo[5,1-c][1,2,4]benzotriazin-4(1H)one werden über Oxime in einerSemmler-Wolff-Reaktion in die tetracyklischen aromatischen Amine4 umgewandelt. In einerSchmidt-Reaktion wurden dieselben Ketone in ein Gemisch aus Amin4 und Lactam3 übergeführt. Synthesen von halogensubstituierten Pyrazolo[3,4-b]pyridinen und photochemische Umwandlung von 3-Azidopyrazolo[3,4-b]pyridin werden beschrieben.相似文献
998.
近年来有不少报道从事于生理活性Drimane类倍半萜的合成,较多采用了分子间Diels-Alder反应来建立Drimane的骨架。本文首次采用内分子Diels-Alder反应作为关键反应合成了Drimane类化合物。同时还在引入了手性诱导基团后,首次完成了从无手性的原料化合物β-紫罗兰酮至光学活性(-)-drimenin1的不对称合成。 相似文献
999.
1000.
Czakis-Sulikowska D. Malinowska A. Łuczak A. 《Journal of Thermal Analysis and Calorimetry》2004,78(2):461-471
Two lactates and four new mixed ligand complexes with formulae Co(lact)2·2H2O, Ni(lact)2·3H2O, Co(4-bpy)(lact)2, Co(2,4'-bpy)2(lact)2, Ni(4-bpy)(lact)2·2H2O and Ni(2,4'-bpy)2(lact)2 (where 4-bpy=4,4'-bipyridine, 2,4'-bpy=2,4'-bipyridine, lact=CH3CH(OH)COO-) were isolated and investigated. The thermal behaviour of compounds was studied by thermal analysis (TG, DTG, DTA). In the
case of hydrated complexes thermal decomposition starts with the release of water molecules. The compounds decompose at high
temperature to metal(II) oxides in air. A coupled TG-MS system was used to analyse the principal volatile products of thermolysis
and fragmentation processes of obtained complexes.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献