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1.
Garcia Ruano JL Alcudia A del Prado M Barros D Maestro MC Fernandez I 《The Journal of organic chemistry》2000,65(10):2856-2862
The addition of the lithium anions derived from (R)- and (S)-methyl and -ethyl p-tolyl sulfoxides to (S)-N-benzylidene-p-toluenesulfinamide provides an easy access route to enantiomerically pure beta-(N-sulfinyl)amino sulfoxides. Stereoselectivity can be achieved when the configurations at the sulfur atoms of the two reagents are opposite (matched pair), thus resulting in only one diastereoisomer, even for the case in which two new chiral centers are created. The N-sulfinyl group primarily controls the configuration of the carbon bonded to the nitrogen, whereas the configuration of the alpha-sulfinyl carbanion seems to be responsible for the level of asymmetric induction, as well as for the configuration of the new stereogenic C-SO carbon in the reactions with ethyl p-tolyl sulfoxides. An efficient method for transforming the obtained beta-(N-sulfinyl)amino sulfoxides into optically pure beta-amino alcohols, based on the stereoselective non-oxidative Pummerer reaction, is also reported. 相似文献
2.
3.
Garcia Ruano JL Alemparte C Martin Castro AM Adams H Rodriguez Ramos JH 《The Journal of organic chemistry》2000,65(23):7938-7943
The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles. 相似文献
4.
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
5.
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
6.
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
7.
The space group of alpha(')-NaV2O5 turns below T(c) = 34 K from Pmmn with all V sites equivalent, into Fmm2 with three independent vanadium sites per layer. This is incompatible with models of charge ordering into V4+ and V5+. Our structure determination indicates that the phase transition consists of a charge ordering with three distinct valence states, formally V4+, V4.5+, and V5+. The singlet formation is not associated with dimerization on the spin ladder, but with the formation of spin clusters. Finally, we ascribe the quadrupling of the c axis to the large polarizability of the V2O5 skeleton. 相似文献
8.
Acoustic performance in ultrasonic transmitters can be improved by means of a suitable electrical driving response and matching/tuning networks. It is important to predict this electrical response, but doing so is not easy because it departs notably from the nominal pattern with the loading probes. In practice, the analysis of HV pulser spikes in NDE applications requires fairly complex models in the transient regime and, in addition, non-linear problems could arise, especially in the case of tuned transmitters. In this paper, the most relevant influences of loading characteristics of NDT ultrasonic probes on the pulser electrical driving responses are evaluated in time and frequency domains. Conventional pulse generators and typical NDE pulsers are considered. Driving responses are analysed across commercial ultrasonic probes and, alternatively, across similar purely electrical loads. Distinct influences on pulser responses from electrical and motional sections of the probes are identified. All these aspects are studied on the basis of experimental and computer results. 相似文献
9.
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
10.
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