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1.
2.
Results of semiempirical calculations (CNDO/2-FK and MINDO/2 methods) for the σ-π complex problem on protonated benzene are given and compared with previous ones. The semiempirical methods were chosen according to the agreement of their results with new theoretical energy data (EHF + Ekorrel) concerning the classical–nonclassical problem of protonated ethylene. By these methods the corresponding part of the energy surface of the benzene/H+ system is simulated. The stationary points of this surface are found by a gradient method with complete optimization of the geometry. On the basis of this method we determined the energy profile of a reaction coordinate between the classical (σ-complex) and nonclassical (π-complex) cation. The so called strong π-complex is a saddle point between two σ-complex minima and can be interpreted as transition state of 1,2-proton shifts. Hypotheses for possible minimum energy paths of electrophilic attacks in the given region of the surface are discussed. 相似文献
3.
Basic Aluminium Salts and their Solutions. XI. 27Al-NMR Studies Comparing the Mineral Zunyite and Basic Aluminium Salts of Tridecameric Al-oxo-hydroxo-aquo-Cations Solid-state high resolution 27Al NMR studies of basic aluminum sulphate and the mineral zunyite, both containing tridecameric Al-oxo-hydroxo groups, show different 27Al spectra. While for zunyite both AlO6 octahedra (0 ppm) and the central AlO4 tetrahedron (69 ppm) are observed in the spectrum, in the case of the basic aluminum sulphate only the tetrahedrally coordinated Al (59 ppm) is detected by NMR. This behaviour is explained by structural data, which indicate stronger distortions of the AlO6 octahedra in the case of the basic aluminum sulphate. The increased shielding of the fourcoordinated Al of the basic sulphate is attributed to an increased ionic character of the Al? O bond in this compound. 相似文献
4.
High-resolution 29Si NMR spectra of zunyite Si5Al13O20 (OH,F)18Cl have been studied by magic-angle sample spinning in combination with high-power proton decouplina and polarization transfer. The isotropic 29Si chemical shift depends mainly on the number of Si-O-Si bridges and the bond angles in these bridges connecting the different SiO4 tetrahedra. 相似文献
5.
On the Preparation and Constitution of the Compound 3 CaO · 3 GeO2 · H2O In the temperature range from 100–∽450°C it is possible to prepare under hydrothermal conditions from equimolar mixtures of CaO and GeO2 the compound 3 CaGeO3 · H2O. By n.m.r. measurements of the solid compound it is shown, that there are only OH groups and no molecular water. It seems to be probable that this compound is a trigermanate of the formula Ca3H2 [Ge3O10]. 相似文献
6.
Si-M.A.S.-N.M.R. Investigations on Crystalline Lead Silicates The isotropic 29Si-n.m.r. chemical shifts of ten crystalline lead silicates with molar ratio PbO:SiO2 between 4:1 and 1:1 has been measured. Starting from the known anion constitution the respective 29Si-n.m.r. signals were assigned to silicate structure units (Qn groups). Decreasing ratio PbO:SiO2 corresponds to significant low-field shifts of the 29Si-n.m.r. signals of definite Qn groups with constant n. This result is of importance to the future investigation of crystalline and vitreous lead silicates with unknown anion constitution. 相似文献
7.
Manfred Meisel Annegrit Rabis Arnd-Rüdiger Grimmer Irmgard Hartwich Regina Bienert Dirk Wulff-molder 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1)
Abstract Previoudy we reported on the preparative use of donorstabilized monometaphosphates, Py.PO2Cl and Py.PS2Cl[1]. 3P MAS investigations as well as X-ray single crystal analysis have been carried out. The isotropic chemical shift of the sulfur compound shows the typical downfield shift (106 ppm) with respect to the oxygen compound The chemical shift anisotropy gives additional information. The relative large spans ω (Py.PO2Cl: 401 ppm, Py.PS2Cl: 461 ppm) [2] reveal strong deviations from tetrahedral symmetry (ω = 0 ppm) in agreement with the structural data. The values of the skew parametem K (0.64 and 0.71 resp.) reflect the trend to axial symmetry (k = ± l). X-ray diffraction and NMR data suggest a structural model corresponding to a concentration of double bond character on the two P-X bonds. This model is consistent with the extremely short P-X bond length (1.449 Å and 1.921 Å rasp.) as well as the large P-X-P bond angles (126.4°and 123.7° resp.). 相似文献
8.
T. Hoger D. Grimmer H. Zacharias 《Applied Physics A: Materials Science & Processing》2007,88(3):449-458
The desorption of NO from a well-characterized, epitaxially grown semiconducting C60 surface is reported. Two different channels are identified in the laser desorption. Both channels yield a comparably high
desorption cross section of σ1=7.0×10-17 cm2 and σ2=5.5×10-17 cm2 for the first and second channel, respectively. The laser desorbed NO molecules are detected with rovibrational state selectivity
by (1+1) REMPI in the -bands. In the first channel the desorbing molecules are highly excited with an average kinetic energy of 〈Ekin〉=174 meV. The rotational population distribution can be fitted by a rotational temperature of Trot=800 K. A rotational–translational coupling is observed, with velocities ranging from 1000 m/s for low to 1300 m/s for high
rotational states. The vibrationally excited population is estimated to be less than 1% of the ground state. The second channel
yields less excited molecules and an almost Boltzmann distributed rotational population with a temperature of Trot=280 K. The apparent velocity distribution derived from the pump-probe delay yields molecules much too slow to be explained
by even a thermal desorption. This desorption is probably caused by a long-lived electronic excitation in the substrate for
which a lifetime of τ≈160 μs is estimated.
PACS 42.62.Fi; 34.50.Dy; 68.49.Df; 68.43.Tj; 79.20.La 相似文献
9.
C,C‐ and N,C‐Coupled Dimers of 2‐Aminotetraphenylporphyrins: Regiocontrolled Synthesis,Spectroscopic Properties,and Quantum‐Chemical Calculations
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Dr. Torsten Bruhn Dipl.‐Chem. Franziska Witterauf Dr. Daniel C. G. Götz Carina T. Grimmer Dipl.‐Chem. Max Würtemberger Prof. Dr. Udo Radius Prof. Dr. Gerhard Bringmann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(14):3998-4006
β,β′‐Bisporphyrins are intrinsically chiral porphyrin dimers with fascinating properties. The configurational stability at their axes can be directed by variation of the central metal atoms. Herein, we present a regioselective functionalization of the monomeric 2‐amino‐tetraphenyl‐porphyrin as a versatile substrate for dimerization by oxidative coupling. By simple variation of the reaction conditions (solvent and oxidant), the oxidation selectively gave either the axially chiral C,C‐coupled diaminobisporphyrin in high yields or, under Ullmann conditions, the twofold N,C‐linked achiral dimer, also in good yields. A generalized mechanism for the coupling reaction is proposed based on DFT calculations. The axially chiral β,β′‐coupled porphyrin dimers were isolated as racemic mixtures, but can be resolved by HPLC on a chiral phase. TDDFT and coupled‐cluster calculations were used to explain the spectroscopic properties of the aminoporphyrins and their dimers and to elucidate the absolute configurations of the C,C‐coupled bisporphyrins. 相似文献
10.