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An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol?1)·T?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH3 group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition. 相似文献
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Abstract Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood. 相似文献
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Calcium batteries are a potentially sustainable, high‐energy‐density battery technology beyond Li ion batteries. Now the development of Ca batteries has become possible with a newly invented Ca electrolyte capable of reversible Ca deposition/stripping at room temperature. 相似文献
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MCl5 (M = Nb, Ta) reacts with 2 equivalents of Me3SiNHCMe3 to give [M(NCMe3)Cl3(NH2CMe3)] from which [M(NCMe3)Cl3(PMe3)2] is obtained on addition of PMe3. One equivalent of Me3SiNHCMe3 reacts with MCl5 in the presence of 3 equivalents of PMe3 to give [M(NCMe3)Cl3(PMe3)2] and PMe3HCl. MCl5 reacts with excess RNH2 (R = CMe3, CHMe2, CH2Me) to give [M(NR)(NHR)Cl2(NH2R)] and 3 equivalents of RNH3Cl. One equivalent of alcohol replaces the amido ligand in [M(NCMe3)(NHCMe3)Cl2(NH2CMe3)] to give [M(NCMe3)(OR)Cl2(NH2CMe3)]2 (M = Nb, R = OCMe3; M = Ta, R = OEt). The structure of [Ta(NCMe3)(μ-OEt)Cl2(NH2CMe3)]2 was determined by single-crystal X-ray diffraction methods. Crystals are triclinic, space group P with a = 9.900(5), b = 10. 161(17), c = 9.017(6) Å and α = 103.91(8), β = 97.77(4), γ = 64.40(7)°. The structure was solved by Patterson and Fourier methods and refined to an R value of 0.062 for 1319 observed data. The TaNimido and TaNamino bond lengths are 1.70(2) Å and 2.28(2) Å, respectively; the bridging TaO bond lengths are 2.01(2) Å and 2.32(2) Å, the longer one lying trans to the imido function. 相似文献
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Reaction of phenylimido tungsten tetrachloride with MeOH and t-butylamine gave the dimeric complexes [W(NPh)(μ-OMe)(OMe)3]2 and [W(NPh)(μ-OMe)(OMe)2Cl]2. With ethanol [W(NPh)(μ-OEt)(OEt)2Cl]2 was formed whereas isopropyl and neopentyl alcohols gave the monomeric complexes [W(NPh)(OR)4(NH2CMe3)](R = CHMe2, CH2CMe3); t-butanol gave [W(NPh)(OCMe3)3Cl(NH2CMe3)] which could not be converted to [W(NPh) (OCMe3)4]. Further reaction of [W(NPh)(μ-OMe)(OMe)3]2 with o-HOC6H4CH = NC6H3Me2(salim-H) gave the salicylaldimine complex [W(NPh)(OMC)3(salim)]. The products were characterised by analytical data, IR, 1H NMR, 13C NMR and mass spectroscopy. The crystal and molecular structures of the title complexes have been determined from single crystal X-ray diffractometer data. Crystals of [W(NPh)(μ-OMe)(OMe)3]2are triclinic with a = 8.473(7), b = 10.776(5), c = 7.683(Å, α = 102.26(3), β = 102.68(4), γ = 71.13(6)°, space group P Crystals of 3) [W(NPh)(OCMe3)3Cl(NH2CMe3) are monoclinic with a = 9.341(2), b = 29.608(7), c = 10.257(2) Å, β = 106.28(2)°, space group, P21/c. Both structures were solved by Patterson and Fourier methods and refined to R = 0.075 for the 1022 observed data of [W(NPh) (μ-OMe)(OMe)3]2 and to R = 0.074. For the 2033 observed data of [W(NPh)(OCMe3)3Cl(NH2CMe3). The former molecule is shown to be a dimer, the two halves of the molecule being related by a centre of symmetry. Both W atoms adopt a distorted octahedral coordination geometry and they are linked by two methoxy bridges. Trans to one of the bridging donors is the phenyl imido group with a WN bond length of 1.61(4) Å; the remaining coordination sites are filled with methoxy groups. The structure of W(NPh)(OCMe3)3 Cl(NH2CMe3) is monomeric with the phenylimido group trans to the NH2CMe3 ligand in a distorted octahedral coordination geometry. Remaining sites are filled with the chloride and 3 OCMe3 ligands. The WN (imido) bond length is 1.71(2) Å, whilst WN(amine) is 2.40(2) Å 相似文献
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Lein M Harrison JA Nielson AJ 《Dalton transactions (Cambridge, England : 2003)》2011,40(40):10731-10741
For the d(0) complex [{Zr(CpSiMe(2)H)Cl(3)}(2)] which contains a linear Si-H···Zr interaction across the dimer, DFT calculations are in good agreement with X-ray structures. The BP86 functional shows a slightly stronger interaction than B3LYP but for qualitative purposes either functional is sufficient. QTAIM analysis shows a bond critical point (bcp) for the interaction, a small negative value for the total energy density [H((r))] and the H atomic basin decreases in energy, E(H), and atomic volume compared to the free ligand. NBO analysis showed E(2) for Si-H σ to Zr(dz(2)) donation at 42.8 kcal mol(-1) and a 34% spatial overlap for the interaction consistent with an inverse hydrogen bond. The Wiberg bond index for the interaction is 0.1735 (0.7205 for the Si-H bond), ν((Si-H)) and (1)J((Si-H)) at 2060 cm(-1) and 145.4 Hz compared to 2183 cm(-1) and 172.1 Hz in the free ligand. Using a "synthesis by computation" approach to forming like complexes, similar features were found for [{Hf(CpSiMe(2)H)Cl(3)}(2)]. The titanium complex [{Ti(CpSiMe(2)H)Cl(3)}(2)] does not contain any Si-H···Ti interaction as rotation about the C-Si bond of the ligand occurs to place the Si-H bond hydrogen closer to a terminal chloro ligand across the dimer. An increase in electron density on the metal in the d(2) complex [{Mo(CpSiMe(2)H)Cl(3)}(2)] results in a stronger interaction with a distinct QTAIM analysis bcp [ρ((r)) 0.0448 a.u.], a small negative value for H((r)) and a much reduced H atomic volume. NBO analysis shows E(2) for Si-H σ to Mo(dz(2)) donation at 143.1 kcal mol(-1) and a 29% spatial overlap. Mo(dz(2)) to Si-H σ* donation (back donation) is minimal [E(2) 1.3 kcal mol(-1), ~1% spatial overlap]. The Wiberg bond index is 0.3114 (0.5667 for the Si-H bond), ν((Si-H)) 2015 cm(-1) and (1)J((Si-H)) 120.6 Hz. 相似文献
9.
C.M. Sharts H.R. Reese Kenneth A. Ginsberg Frances K. Multer Margot D. Nielson A.Gerson Greenburg Gerald W. Peskin David M. Long 《Journal of fluorine chemistry》1978,11(6):637-641
The solubility of oxygen in aqueous fluorocarbon emulsions has been measured directly for several perfluorocarbons and monobromo or monoiodo-perfluorocarbons. The measured oxygen solubilities are consistent with results for the solubility of oxygen in neat liquid perfluorinated organic compounds. 相似文献
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