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35.
P. Herzog U. Dämmrich K. Freitag C. -D. Herrmann K. Schlösser 《Zeitschrift für Physik B Condensed Matter》1986,64(3):353-356
Nuclear magnetic resonance of82Br oriented at low temperature in iron has been observed with a sample prepared by ion implantation atT<0.2 K. The asymmetric resonance signal can be decomposed in a broad background signal and a narrow line of FWHM=1.8 (4) MHz which can be attributed to82Br in undisturbed substitutional sites of Fe. From the center frequency of this narrow line (B
ext=0)=201.86(13) MHz we derive the magnetic hyperfine field asB
hf(BrFe)=81.38(6) T. This value is considerably larger than the result of theoretical calculations. 相似文献
36.
Wolfgang A. Herrmann Carl Krüger Richard Goddard Ivan Bernal 《Journal of organometallic chemistry》1977,140(1):73-89
μ-Carbonylbis(carbonyl-ν5-cycopentadienylrhodium)(Rh—Rh) reacts with N-methyl-and N-ethyl-N-nitrosourea in boiling benzene to yield the dinuclear, diamagnetic, neutral rhodium complexes μ-methylene- (A) and μ-ethylidenebis(carbonyl-η5-cyclopentadienylrhodium)(Rh—Rh) (B), respectively. Deuterium labelled experiments prove the origin of the metal-stabilized methylene ligand to be the alkyl group of the organic precursor. This new method of preparation of transition metal—methylene complexes may be used as an alternative to the commonly used diazo method; the latter method was shown to work with diazodiethylmalonate and dicarbonyl-η5-cyclopentadienylrhodium, the reaction yielding μ-bis(ethoxycarbonyl)methylenebis(carbonyl-η5-cyclopentadienylrhodium)(Rh—Rh).Compound A crystallizes in the triclinic system, P, and with cell constants of a 803.42(5), b 909.98(6), c 938.81(2) pm, α 74.402(3), β81.923(3), and γ 83.685(6)°. The unit cell volume and the calculated density are 651.6 Å3 and 2.069 g cm-3, for one molecule in the asymmetric unit. The molecular geometry of μ-CH2[η5-C5H5Rh(CO)]2 was established from 2718 unique reflections collected with a computer-controlled diffractometer and refined to a final R(F) = 0.0379. The molecular parameters derived from the single-crystal X-ray study conform to a remarkable degree with those found for μ-CO[η5-C5H5Rh(CO)]2. Thus, the bridging ligands CH2 and CO seem to be analogous in their effects on the structural characteristics of the molecular framework of the two molecules. 相似文献
37.
Wolfgang A. Herrmann 《Angewandte Chemie (International ed. in English)》1978,17(11):800-812
In recent years, aliphatic diazo compounds have proved to be more and more versatile as reagents in the preparative chemistry of organometallic complexes. As readily accessible compounds, they are not only suitable for the synthesis of known kinds of metal complexes but also open fresh routes to novel complex systems. The comparatively new field of diazoalkane complex chemistry exhibits numerous unexpected and novel reactions, and introduces interesting and promising aspects into the chemistry of carbonylmetal compounds. 相似文献
38.
Genosar L Lasitza T Gepshtein R Leiderman P Koifman N Huppert D 《The journal of physical chemistry. A》2005,109(21):4852-4861
The pressure dependence of the excited-state proton dissociation rate constant of four photoacids, 2-naphthol-6,8-disulfonate (2N68DS), 10-hydroxycamptothecin (10-CPT), 5-cyano-2-naphthol (5CN2), and 5,8-dicyano-2-naphthol (DCN2), are studied in methanol. The results are compared with the results of the pressure dependence study we recently conducted for several photoacids in water, ethanol, and propanol. The pressure dependence is explained using an approximate stepwise two-coordinate proton transfer model. The increase in rate, as a function of pressure, manifests a strong dependence of proton tunneling on the distance which decreases with an increase of pressure between the two oxygen atoms involved in the process. The decrease in the proton transfer rate with increasing pressure reflects the dependence of the reaction on the solvent relaxation rate. We found that, for the relatively weak photoacids 2N68DS, 10-CPT, and 5CN2, the proton transfer rate constant increases by a factor of about 5-8 at a pressure of about 1.5 GPa. For a strong photoacid like DCN2, the rate increase was only by a factor of 2. 相似文献
39.
S. Herrmann W. Vonau F. Gerlach H. Kaden 《Analytical and bioanalytical chemistry》1998,362(2):215-217
A new sensor module is developed for the in-situ control of waters, especially surface waters. Complex miniaturized sensor technology is used for the determination of the parameters pO2, pH, pNO3, pCl, pPO4, pNH3 or pNH4 and conductivity. Miniaturization of sensors results in small sample volumes and small volumes of calibration solution required. Results of testing this sensor module are described. The special features of this apparatus are its compact construction and its optimum functioning capability under flow conditions. 相似文献
40.
The halothane???acetone and fluoroform???acetone complexes are studied using the second‐order Møller–Plesset (MP2) method with a cc‐pVTZ basis set and the density functional theory (DFT) method with a TZVP basis set. Whereas halothane exhibits a small red shift upon complexation, fluoroform shows a pronounced blue shift. To explain this difference in behavior, we perform symmetry‐adapted perturbation theory (SAPT) and natural bond orbital (NBO) analyses. Although the composition of the total stabilization energy of each complex is different, that alone does not provide a satisfactory explanation for the difference in the spectral shifts. This difference is interpreted as a result of the interplay of the hyperconjugation and rehybridization mechanisms. The small and surprising red shift of the C? H stretching frequency of halothane, which resulted from the complexation of this species with acetone,is explained by the compensation of the two above‐mentioned mechanisms. On the other hand, the fluoroform???acetone complex exhibits a blue shift of the C? H stretching frequency upon complexation, the most likely reason for this shift being a concerted occurrence of the hyperconjugation and rehybridization mechanisms. The calculated shift of the C? H stretching vibration frequencies of halothane (+27 cm?1) agree with the experimental value of +5 cm?1. 相似文献