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61.
Heterometallic Complexes with E6 Ligands (E = P, As) The reaction of [Cp*Co(μ-CO)]2 1 with the sandwich complexes [Cp*Fe(η5-E5)] 2 a: E = P, 2 b: E = As in decalin at 190°C affords besides [CpCo2E4] 4: E = P, 7: E = As and [CpFe2P4] 5 the trinuclear complexes [(Cp*Fe)2(Cp*Co)(μ-η2-P2)(μ31:2:1-P2)2] 3 as well as [(Cp*Fe)2(Cp*Co)(μ32:2:2-As3)2] 6 . With [Mo(CO)5(thf)] 3 and 6 form in a build-up reaction the tetranuclear clusters [(Cp*Fe)2(Cp*Co)E6{Mo(CO)3}] 10: E = P, 11: E = As. 3, 6 and 11 have been further characterized by an X-ray crystal structure determination.  相似文献   
62.
The reactions of Ge2(C6H5)6 with HCl and HBr lead in nearly quantitative yields to the 1,1,2,2-tetrahalo derivatives Cl2(C6H5)GeGe(C6H5)Cl2 (I) and Br2(C6H5)GeGe(C6H5)Br2 (II), resp. The Si?Ge bond of (C6H5)3SiGe(C6H5)3 is cleaved under the conditions of hydrohalogenation. The vibrational spectra of Ge2Br6, Ge2(C6H5)6, I, and II are reported. The influence of vibrational coupling on ν GeGe in these compounds is discussed in detail, including vibrational calculations.  相似文献   
63.
Preparation and Crystal Structure of Cadmium Azide Cd(N3)2 Solvent free, binary cadmium azide was synthesized by the reaction of cadmium carbonate and a 24 weight% solution of HN3 in water. Cadmium azide is a colorless, crystalline powder which is highly sensitive to percussion and heat. Caution, the manipulation of Cd(N3)2 is very dangerous! The crystal structure was solved by single‐crystal methods and the phase purity was verified by a Rietveld refinement (Cd(N3)2, Pbca, no. 61; a = 7.820(2), b = 6.440(2), c = 16.073(3) Å; Z = 8, 1174 independent reflections, 64 parameters, R1 = 0.022). Cadmium azide crystallizes in a new structure type. In the crystal there are edge‐sharing Cd2(N3)10 double octahedrons which are further connected to other units by azide bridges. Vibrational spectroscopic investigations (Raman an IR) are discussed with respect to the crystal structure data.  相似文献   
64.
Equilibrium Measurements by the Transport Method. Determination of the Enthalpie of Formation ΔH°(NbOCl2,f) by Chemical Transport in the Diffusion Tube By means of chemical transport in an ampoule with a well defined diffusion path the equilibrium NbOCl2,s + NbCl5,g ? NbOCl3,g + NbCl4,g has been investigated. Introducing a reaction entropy ΔS = 45 cl one gets ΔH = 38(±2) kcal/formula weight and ΔH0(NbOCl2,s)= ?187,6 kcal/mol.  相似文献   
65.
The second virial coefficients of homonuclear three-centerLennard-Jones molecules are calculated with various parameters of the isosceles triangle connecting the three sites. A special effort is made to establish the reducedBoyle temperaturesT B and the values of the second virial coefficients atT/T B=0.3 for the sake of comparison with one- and two-centerLennard-Jones molecules. It is shown that it is possible to find parameter values of the interaction potential of one- and two-centerLennard-Jones molecules which give very similar values of second virial coefficients forT/T B0.3, and the equivalence conditions are established. These conditions might not only give a basis for a microscopic scaling of state variables, but also some restrictions for the validity of the group contribution concept.Presented in part at the DFG-Colloquium at Paderborn, 19th April 1982, and at the 5th Conference on Mixtures of Nonelectrolytes and Intermolecular Interactions, April 18–22, 1983, at Halle (GDR).  相似文献   
66.
The performance of an energy sensitive, niobium superconducting tunnel junction (STJ) detector is investigated by measuring the pulse height produced by impacting molecular and atomic ions at different kinetic energies. Ions are produced by laser desorption and matrix-assisted laser desorption in a time-of-flight mass spectrometer. Our results show that the STJ detector pulse height decreases for increasing molecular ion mass, passes through a minimum at around 2000 Da, and then increases with increasing mass of molecular ions above 2000 Da. The detector does not show a decline in sensitivity for high mass ions as is observed with microchannel plate ion detectors. These detector plus height measurements are discussed in terms of several physical mechanisms involved in an ion-surface collision.  相似文献   
67.
Abstract —The time-dependent rotational relaxation of Rhodamine 6G in fresh and dried human blood serum was investigated using picosecond phasefluorometry. Measurements were also carried out in aqueous solutions of amino acids, glucose, urea, and bovine serum albumin to evaluate our model for the interactions. It is shown that the distribution of Rhodamine 6G between the aqueous and the protein phase of the blood serum strongly depends on protein concentration and temperature.  相似文献   
68.
Thiomorpholine as well as alkyl substituted thiomorpholines and their Sdioxides, respectively, are transformed into the corresponding N-Aminothiomorpholines by nitrosation (1–5) followed by the reduction with zinc in acetic acid/acetic acid anhydride under simultaneous formation of the corresponding N-acetyl derivates, and hydrolysis by hydrochloric acid (6–9). Examples of this method are described. 4-Aminothiomorpholines and their Sdioxides react with aldehydes or ketones to give azomethines (10–31). Acylation with mono-and dicarbonic acid chlorides leads to the N-acyl derivatives32–44.Mannich condensation is also possible. By oxidation with yellow mercury oxide tetracenes are formed (46–47).
Teil der DissertationM. Schmitz, Techn. Hochschule Aachen, 1975.  相似文献   
69.
 Distillation as a way of sample digestion has been combined with on-line RP C18 preconcentration and HPLC-UV-PCO-CVAAS (high performance liquid chromatography – ultra violet – post column oxidation – cold vapour atomic absorption spectrometry) for the determination of methylmercury at background levels in sediments, soils and fish tissue. To prove the accuracy of this method, it was applied to sediment and fish tissue reference materials. The results correspond with the reference values within their error ranges. Excellent recoveries (92–95%) were obtained for the sediment samples by means of the standard addition method. The standard deviations of the sediment samples were within an acceptable range (7.2–12.5%), those of the fish samples were substantially lower (3.4–5.0%). The detection limit is 0.04 ng/g for 1 g sample weight. Received: 23 November 1995/Revised: 16 April 1996/Accepted: 20 April 1996  相似文献   
70.
N-heterocyclic olefins (NHOs), relatives of N-heterocyclic carbenes (NHCs), exhibit high nucleophilicity and soft Lewis basic character. To investigate their π-electron donating ability, NHOs were attached to triarylborane π-acceptors (A) giving donor (D)–π–A compounds 1 – 3 . In addition, an enamine π-donor analogue ( 4 ) was synthesized for comparison. UV–visible absorption studies show a larger red shift for the NHO-containing boranes than for the enamine analogue, a relative of cyclic (alkyl)(amino) carbenes (CAACs). Solvent-dependent emission studies indicate that 1 – 4 have moderate intramolecular charge-transfer (ICT) behavior. Electrochemical investigations reveal that the NHO-containing boranes have extremely low reversible oxidation potentials (e.g., for 3 , =−0.40 V vs. ferrocene/ferrocenium, Fc/Fc+, in THF). Time-dependent (TD) DFT calculations show that the HOMOs of 1 – 3 are much more destabilized than that of the enamine-containing 4 , which confirms the stronger donating ability of NHOs.  相似文献   
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