Linear trigermoxanes, R1 RGeOGe(R3)2OGeRR1, a new series of organogermanium compounds, were synthesized by reaction of a lithium organogermanolate with a suitable organogermanium dihalide. With alkyl or phenyl substituents, these trigermoxanes are structurally unstable viscous oils, due to redistribution reactions. When R3 substituents are bulky groups, such as mesityl, trigermoxanes are thermally and structurally stable oils; depending on the R1 and R2 substituents their viscosities lie in the range 240 to more than 1500 cPo (mPa s) at 20°C. When both terminal germanium atoms are substituted with two mesityl groups, trigermoxanes are stable glassy solids. 相似文献
About Perrhenates. 3 On the Structure of the Mesoperrhenate Na3[ReO5] By tempering powder samples (prepared from mixtures of binary oxides: Na2O2/ReO2 and Na2O/ReO3 respectively, Na : Re = 3 : 1, Ar and O2 atmosphere respectively, 400–450°C, corundum boat) in a closed Ag cylinder (500–550°C, 10 d) yellow single crystals of Na3ReO5, sensitive to moisture, were grown. The compound crystallizes trigonal, space group P31, P32 respectively, with a = 5.544(1), c = 13.580(7) Å, Z = 3, drö. = 4.62 g/cm3. The crystal structure [4-circle diffractometer data, 1091 I0(hkl), AgKα, R = 6.14, Rw = 6.08%] is characterized by “isolated” bipyramids ReO5. Na+ ions are occupying all the tetrahedral (Na2, Na3) and octahedral (Na1) holes of the pseudocubic face centred (c/a = 2.441) Re part of the lattice; resulting in a Na3Re kation framework corresponding to the Li3Bi type of structure. Effective Coordination Numbers (ECoN), the Madelung Part of Lattice energy (MAPLE) and the charge distribution (CHARDI) are computed and discussed. 相似文献
The SIBFA procedure (Sum of Interactions Between Fragments computedAb initio, Ref [1]) is extended to the study of the conformational behavior of representative molecules containing amide nitrogens and carbonyl and carboxylate oxygens. The molecules studied are C- and N-ethylammonium formamide, C- and N-ethanol-formamide, ethylammonium formate and ethanolformate. The cases investigated include interactions of the types which occur between functional groups in proteins or ionophores. The accuracy of the procedure, assessed by comparing the results to those of correspondingab initio SCF computations, is very satisfactory. An application of the procedure to study the conformation of the glycyl and alanyl dipeptides as a function of the backbone torsional angles and is presented. 相似文献
Summary A possibility of obtaining insoluble gels with the help of freezing-thawing procedures was demonstrated on an example of aqueous solutions of a thiol-containing poly(acryl amide) derivative. The gel formation was proved to occur as a result of oxidation of free SH groups of polymer chains by water-dissolved air oxygen. 相似文献
Summary Retention indices and their energy equivalents were determined for ten alkylthiazoles analysed on the stationary phases Apiezon
L, Triton X-305 and Carbowax 1000. It was found that the energy contributions of identical alkyl groups to the partial molar
free energy of sorption of a molecule are not equivalent. Smaller energy contribututions are due to the α-position of alkyl
groups with respect to the heteroatoms in the thiazole ring (α-effect). This effect was most pronounced for 2-alkylthiazoles.
Higher sorption energies were found for dimethylthiazoles with two methylgroups in a vicinal position. The retention indices
were predicted for ten other di- and tri-substituted methyl, ethyl and propyl thiazoles on the basis of the so-called α- and
ortho-effects. The predicted values are in good agreement with the experimentally determined values.
Dedicated to Prof. Dr. E. sz. Kováts (Ecole Polytechnique Fédérale de Lausanne) on the occasion of his sixtieth birthday. 相似文献
A new kind of perfluoroalkyl-containing multifunctional groups compound was designed. Treatment of 1H,1H,2H,2H-perfluorooctyltrichlorosilane (4) with allylmagnesium bromide provided key intermediate 1H,1H,2H,2H-perfluorooctyltriallylsilane (2). Hydroboration followed by oxidation, epoxidation and dihydroxylation of 2 gave perfluoroalkyl-containing multifunctional groups compound 1a, 1b and 1c, respectively. 相似文献
A study of the spin lattice relaxation (T1) and the nuclear quadrupole resonance frequency (νQ) gives an important information about the dynamics of molecular groups in molecular solids. In the present paper, we analyze the contributions of the reorientational motion of nitro groups of 2,4-dinitrochlorobenzene to the NQR parameters of the chlorine nucleus in the molecule.
We found two contributions to T1 and νQ due to the onset of the reorientation of nitro groups in the molecule; one of these contributions is mostly due to intermolecular effects in the crystal. For the chlorine nuclei, the efficiency of the modulation mechanism is usually provided by the change of the electric field gradient due to the moving molecular group; this gives us a way of how to assign each contribution to T1 from the ortho and para positions of the NO2 groups in the molecule. It is observed that there are two different potential barriers depending on the position of the nitro groups in the molecule. The behavior in the temperature dependence of the line width shows a thermal history dependence of the molecular crystal. 相似文献
It has been proven qualitatively by a number of authors using variable temperature NMR experiments that most metal carbonyl complexes are nonrigid. A quantitative determination of the ligand exchange frequency ve is often achieved by a line shape analysis or by measurement of the transverse relaxation time T2 using the Carr-Purcell method. In the case of a “very fast” exchange, however, both methods prove unsuccessful. It is shown in this study that a simultaneous fit of IR or Raman spectra on the one hand and NMR spectra on the other can make possible the determination of ve for the “very fast” exchange and can also facilitate the determination of ve in “slow” and “medium” exchange cases considerably. The ligand exchange frequency thus found for Fe(CO)5, 1.1 × 1010s?1, is unexpectedly high; comparison with variable temperature measurements on solid Fe(CO)5, yields similar energy barriers. A mechanism of exchange closely related to the “Berry mechanism” is proposed. Finally the consequences of this surprisingly large ligand exchange rate are discussed with respect to IR band assignments for molecular “fragments” M(CO)x (where x=coordination number, and M is a transition metal, typically lanthanoid or actinoid). 相似文献