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Cai H Chen T Wang X Schultz AJ Koetzle TF Xue Z 《Chemical communications (Cambridge, England)》2002,(3):230-231
Reactions of Ta(NMe2)5 with D2SiR'Ph (R' = Me, Ph) were found to give a dideuteride eta 2-imine complex (Me2N)3Ta(mu-D)2(mu-N-eta 2-N,C-CH2NMe)Ta(NMe2)3(1-d2) through C-H activation of an amide ligand via beta-H abstraction, and the structure of 1 was confirmed by single crystal neutron and X-ray diffraction. 相似文献
206.
The influence of introducing water molecules into a cation-pi complex on the interaction between the cation and the pi system was investigated using the MP2/6-311++G method to explore how a cation-pi complex changes in terms of both its geometry and its binding strength during the hydration. The calculation on the methylammonium-benzene complex showed that the cation-pi interaction is weakened by introducing H(2)O molecules into the system. For example, the optimized interaction distance between the cation and the benzene becomes longer and longer, the transferred charge between them becomes less and less, and the cation-pi binding strength becomes weaker and weaker as the water molecule is introduced one by one. Furthermore, the introduction of the third water molecule leads to a dramatic change in both the complex geometry and the binding energy, resulting in the destruction of the cation-pi interaction. The decomposition on the binding energy shows that the influence is mostly brought out through the electrostatic and induction interactions. This study also demonstrated that the basis set superposition error, thermal energy, and zero-point vibrational energy are significant and needed to be corrected for accurately predicting the binding strength in a hydrated cation-pi complex at the MP2/6-311++G level. Therefore, the results are helpful to better understand the role of water molecules in some biological processes involving cation-pi interactions. 相似文献
207.
Thomas F.O. Lim Jerry K. Myers Greg. T. Rogers Paul Ronald Jones 《Journal of organometallic chemistry》1977,135(2):249-259
The regioselectivity of the hydroboration of the methylchlorovinylsilanes, ClnMe3?nSiCHCH2 (n= 0 ? 3), has been investigated using BH3←THF, 9-BBN, disiamyl- and dicyclohexylborane. Methylation of the adducts with methylmagnesium bromide is complicated by formation of tetraalkylboronates. Alkaline hydrogen peroxide oxidation of the boronates gives reasonable yields of the corresponding α- and β-trimethylsilylethanols forn= 0 and 1. Forn= 2 and 3, conversion of the adducts to the corresponding α- and β- deuteroethylsilanes by treatment with excess sodium methoxide in methanol-0-d provides a more effective means of derivatization. Addition of the alkenes,n= 2 or 3, to excess BH3←THF givesca. 90% of the α-boro-organo-chlorosilanes. For all of the alkenes, the dialkylboranes giveca. 80% of the β-boron adducts. 相似文献
208.
6-Diazopenicillanates react with allylic sulphides, selenides and bromides, to give 6,6-disubstituted penicillanates [2,3]-sigmatropic rearrangements. 相似文献
209.
Thomas Armbruster 《Journal of solid state chemistry》1981,36(3):275-288
The phase relations in the system NiOTiO2 were studied between 1000 and 1600°C using quenched powder specimens, DTA runs, and single crystal diffusion couples. Quenching experiments establish the stable phases TiO2 (rutile), NiTiO3 an ilmenite structure type, Ni2(1+x)Ti1?xO4 (x ≥ 0.16), a cation-excess spinel, and Ni1?2xTixO (rocksalt structure type). DTA runs reveal the existence of an additional nonstoichiometric ilmenite phase Ni1?2xTi1+xO3 (x ≤ 0.03) above 1260°C. In quenched (1500, 1450°C) or slowly cooled single crystal diffusion couples, mutual oriented exsolutions occur in the rutile crystal and in the ilmenite diffusion zone. Orientation relations are: {101}rutile{1120}ilmenite; ∥010〉rutile∥00.1〉ilmenite. The cation-excess spinel decomposes below 1375°C into oriented intergrowth of NiTiO3 (ilmenite) and NiO: {111}NiO{0001}NiTiO3; ∥110〉NiO∥21.0〉NiTiO3. 相似文献
210.
The sensitivity of six mammalian cell strains to either germicidal (254 nm) or artificial "solar" simulated radiation was tested. The solar simulator used had an output similar, in some respects, to natural sunlight. Cellular capacity for Herpes simplex virus production was used as the assay procedure. The tested cells were a strain of African green monkey kidney cells and five human skin fibroblast cell strains. The latter included a "normal" cell strain, and four photosensitive cell strains; three of which were strains of xeroderma pigmentosum cells, and one strain of Bloom's syndrome cells. When comparing the D10 values, the different cell strains varied by a factor of six in response to germicidal radiation, but only by a factor of two to artificial "solar" simulated radiation. The relative sensitivity of the cells to either type of radiation also varied from 1.7 to 10.9. Large variations in response occurred even among the xeroderma pigmentosum cell strains. These responses suggest that mammalian cell sensitivity to 254 nm radiation may not be a true indicator of a cell's responses to natural sunlight. 相似文献