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141.
The 17-electron species [M(CO)5χLχ] (M Mn, Re, χ 0; M Mn, Re; L Ph3P, χ 1, 2; M Mn, Re; L (o-MeC6H4O)3P, χ 2; M Mn; L (p-ClC6H4O)3P, (PhO)3P, χ 2; M Mn; L P(OMe)3, χ 3) have been generated by one electron oxidation of the corresponding anions and show typical radical reactivity, undergoing dimerisation or hydride abstraction in reactions controlled by steric effects. Evidence is presented for the source of the hydrogen atom. The 19-electron species [M(CO)3(η7-C7H7)]? (M Cr, Mo) and [Fe(CO)3(η5-C6H7)]?, generated by reduction of the corresponding cations, undergo dimerisation at the organic ligand. Similar treatment of [Fe(CO)2-L(η-cp)]+ (L CO, PPh3, P(OPh)3, Me2CO) yields [Fe2(CO)4(η-cp)2] and these reduction reactions are rationalised in terms of the nature of the HOMO in the intermediate radical. Similar reduction of [Rh(diphos)2]+ yield the 17-electron intermediate [Rh(diphos)2] and this also undergoes hydrogen abstraction. 相似文献
142.
trans-PtH2[As(t-Bu)3]2 was prepared in very good yield by afacile reaction of K2PtC14 with As(t-Bu)3 in alkaline ethanol. Treatment of trans-PtH2[As(t-Bu)3]2 with CF3CO2H or HCI afforded trans-PtH(O2CCF3)[As(t-Bu)3]2 or trans-PtHCl[As(t-Bu)3]2. respectively, in almost quantitative yield. 相似文献
143.
The coalescence temperature for the C-methyl peaks in the NMR spectra of hydrazones of acetone are above 200°, indicating an energy barrier for syn-anti isomerization greater than 28 kcal mole?1. the presence of halogenated compounds decreases the energy barrier, due to the formation of a charge transfer complex between the hydrazone acting as a donor and the halogenated compound acting as the electron acceptor. 相似文献
144.
The reaction of tert-butylamine, isoxazolidine and hydrazine with N-[(3-chloropropyl)oxy]phthalimide is investigated. A convenient synthesis of oxazolidine is described. 相似文献
145.
The phase diagram for the binary system K2CrO4CaCrO4 has been determined for CaCrO4 concentrations up to 60 mole%, using the techniques of differential thermal analysis, X-ray diffraction, and drop calorimetry. Essential features of the phase diagram are: the solid-solid phase transition for pure K2CrO4 at 670°C, β-K2CrO4 ? α-K2CrO4; a eutectoid reaction at 14 mole% CaCrO4 and 548°C, β-K2CrO4 ? α-K2CrO4 + K2CrO4 · CaCrO4; a peritectoid event at 50 mole% CaCrO4 and 640°C, β-K2CrO4 + CaCrO4 ? K2CrO4 · CaCrO4; and a eutectic reaction at 51 mole% CaCrO4 and 678°C, L ? β-K2CrO4 + CaCrO4. X-ray diffraction studies lead to the determination of the unit cell dimensions for the K2CrO4 · CaCrO4 double salt, a C-centered monoclinic form with a0 = 7.615(6) Å, b0 = 22.797(15) Å, c0 = 9.777(9) Å, β = 115.45(5)°. 相似文献
146.
U. Berg R. Isaksson J. Sandström U. Sjöstrand A. Eiglsperger A. Mannschreck 《Tetrahedron letters》1982,23(41):4237-4240
(+)- and (?)- as well as (+)- and (?)- were partially separated by liquid chromatography on triacetylcellulose; racemizations resulted in the barriers (Table 2) to rotation via planarized transition states. 相似文献
147.
The crystal structure of a second high-pressure copper vanadate phase, CuVO3(II), has been determined and refined by full-matrix least-squares procedures using automatic diffractometer data to a residual R = 0.042 (Rw = 0.051). The space group is rhombohedral, , with hexagonal unit cell a = 4.966(2) and c = 14.084(5) Å [aR = 5.501(2) Å and α = 53.66(3)°]. The structure is the fully ordered ilmenite-type and, on the basis of published magnetic data and the interatomic distances, the valence distribution Cu+V5+O3 is proposed. This represents a unique example of Cu+ in an octahedral environment. 相似文献
148.
Heat transfer from a plasma flow to a metallic or nonmetallic spherical particle is studied in this paper for the extreme case of free-molecule flow regime. Analytical expressions are derived for the heat flux due to, respectively, atoms, ions, and electrons and for the floating potential on the sphere exposed to a two-temperature plasma flow. It has been shown that the local or average heat flux density over the whole sphere is independent of the sphere radius and approximately in direct proportion to the gas pressure. The presence of a macroscopic relative velocity between the plasma and the sphere causes substantially nonuniform distributions of the local heat flux and enhances the total heat flux to the sphere. The heat flux is also enhanced by the gas ionization. Appreciable difference between metallic and nonmetallic spheres is found in the distributions along the oncoming flow direction of the floating potential and of the local heat flux densities due to ions and electrons. The total heat flux to the whole sphere is, however, almost the same for these different spheres. For a fixed value of the electron temperature, the heat flux decreases with increasing temperature ratio Te/Th. 相似文献
149.
Formylation is one of the newly discovered post-translational modifications in lysine residue which is responsible for different kinds of diseases. In this work, a novel predictor, named predForm-Site, has been developed to predict formylation sites with higher accuracy. We have integrated multiple sequence features for developing a more informative representation of formylation sites. Moreover, decision function of the underlying classifier have been optimized on skewed formylation dataset during prediction model training for prediction quality improvement. On the dataset used by LFPred and Formator predictor, predForm-Site achieved 99.5% sensitivity, 99.8% specificity and 99.8% overall accuracy with AUC of 0.999 in the jackknife test. In the independent test, it has also achieved more than 97% sensitivity and 99% specificity. Similarly, in benchmarking with recent method CKSAAP_FormSite, the proposed predictor significantly outperformed in all the measures, particularly sensitivity by around 20%, specificity by nearly 30% and overall accuracy by more than 22%. These experimental results show that the proposed predForm-Site can be used as a complementary tool for the fast exploration of formylation sites. For convenience of the scientific community, predForm-Site has been deployed as an online tool, accessible at http://103.99.176.239:8080/predForm-Site. 相似文献
150.
In the analysis of gene expression profiles, the number of tissue samples with genes expression levels available is usually small compared with the number of genes. This can lead either to possible overfitting or even to a complete failure in analysis of microarray data. The selection of genes that are really indicative of the tissue classification concerned is becoming one of the key steps in microarray studies. In the present paper, we have combined the modified discrete particle swarm optimization (PSO) and support vector machines (SVM) for tumor classification. The modified discrete PSO is applied to select genes, while SVM is used as the classifier or the evaluator. The proposed approach is used to the microarray data of 22 normal and 40 colon tumor tissues and showed good prediction performance. It has been demonstrated that the modified PSO is a useful tool for gene selection and mining high dimension data. 相似文献