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Harald Stueger Markus Braunwarth Gottfried Fuerpass Judith Baumgartner Robert Saf 《Monatshefte für Chemie / Chemical Monthly》2006,137(5):595-603
Summary. The previously unknown ruthenio disilanes Rp–Si2Me4–C6H4X (Rp = η5-C5H5Ru(CO)2; X = H, Br, –CHO, CH=C(CN)2) were synthesized from ClSi2Me4C6H4X (X = H, Br) and Rp− using conventional chemical methods. Trends in the UV/Vis absorption spectra indicate strong electronic coupling within the
Rp–Si–Si–Caryl fragment and, therefore, closely resemble the ones observed for the corresponding iron complexes. The four compounds however,
were shown to be less sensitive towards UV irradiation. The crystal structure of Rp–Si2Me4–C6H4CH=C(CN)2 was determined by X-ray diffraction and exhibits an all-trans-array of the Ru–Si–Si–Caryl moiety, what is a basic requirement for optimal through-bond interaction. 相似文献
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Huang S Xiao Z Wang F Zhou J Yuan G Zhang S Chen Z Thiel W von Ragué Schleyer P Zhang X Hu X Chen B Gan L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(18):5449-5456
[60]Fullerene mixed peroxides C60(O)(OOtBu)4 exhibit chemo- and regioselective reactions under mild conditions. The epoxy moiety is opened by ferric chloride to form vicinal hydroxy chloride C60Cl(OH)(OOtBu)4. BF3 is also effective in opening the epoxy moiety. The O-O bond of the fullerene mixed peroxide is cleaved by aluminum chloride to form both [5,6]- and [6,6]-fullerene hemiketals (oxohomo[60]fullerenes). A Hock-type rearrangement is proposed for the formation of the hemiketals, in which a fullerene C-C bond is cleaved. Lewis acids and/or visible light can initiate isomerization of the hemiketal isomers. Single-crystal X-ray analysis and theoretical calculations confirmed the results. 相似文献
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Density functional theory and complete active space self-consistent field computations are applied to elucidate the singlet diradical character of square planar, diamagnetic nickel complexes that contain two bidentate ligands derived from o-catecholates, o-phenylenediamines, o-benzodithiolates, o-aminophenolates, and o-aminothiophenolates. In the density functional framework, the singlet diradical character is discussed within the broken symmetry formalism. The singlet-triplet energy gaps, the energy gained from symmetry breaking, the spin distribution in the lowest triplet state, and the form of the magnetic orbitals are applied as indicators for the singlet diradical character. Moreover, a new index for the diradical character is proposed that is based on symmetry breaking. All symmetry breaking criteria show that the complexes obtained from o-catecholates and o-benzodithiolates have the largest and the smallest singlet diradical character, respectively. The singlet diradical character should be intermediate for the complexes derived from o-phenylenediamines, o-aminophenolates, and o-aminothiophenolates. The diradical character of all complexes suggests the presence of Ni(II) central atoms. This is also indicated by the d-populations computed by means of the natural population analysis. 相似文献
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An extraction procedure based on cloud point phase separation of nonionic surfactants was used to remove oil contamination from soils. The detergent employed was Triton X-114, and its clouding behavior was monitored by means of a fluorescence probe. Changes in the I (1)I (3) ratio of pyrene indicated gradual dehydration of the detergent micelles upon heating. The rate of phase separation, and the volume and water content of the micellar phase were determined. In the practical clean-up, 85-98% of the oil present in the soil was found to enter the micellar phase of the separated washing liquid. A 15-min washing time with 3-5% detergent was found to be sufficient for this degree of contaminant removal from soil containing 0.009-0.017% oil, using a liquid:solid ratio of 5:2. The extraction efficiency decreased with increasing carbon content of the soil. The process holds promise for large-scale treatment of oil-polluted soils. 相似文献