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41.
42.
Eight tris(β-diketonate)gallium(III) and seven tris(β-diketonate)-indium(III) complexes M(RCOCH-COR′)3, with R′being difluoromethyl and trifluoromethyl substituents and R′ being methyl, phenyl, aryl, 2′-naphthyl and 2′-thienyl substituents have been studied by nuclear magnetic resonance spectroscopy. The complexes are all nonrigid (fluxional) and their 19F NMR spectra show four resonances in the nonexchanging regions due to cis and trans isomers. A variable low temperature study of these complexes was done for the gallium chelates and activation parameters are calculated. The indium complexes all have nonexchanging regions below ?100°C. The 13C NMR data on the complexes are also reported. 相似文献
43.
H. Michel G. Barci-Funel J. Dalmasso G. Ardisson P. G. Appleby E. Haworth F. El-Daoushy 《Journal of Radioanalytical and Nuclear Chemistry》2001,247(1):107-110
238Pu, 239-240Pu, and 241Am were measured, by -counting after radiochemical separation, in two lake sediment cores. The profiles of these transuranics were compared to those of the fission product 137Cs. Datation of nuclear events and data on behavior of the studied elements were deduced. 相似文献
44.
Haworth NL Sullivan MB Wilson AK Martin JM Radom L 《The journal of physical chemistry. A》2005,109(40):9156-9168
A variety of theoretical procedures, including the high-level ab initio methods G3, G3[CC](dir,full), and W2C//ACQ, have been used to predict the structures and heats of formation of several small calcium-containing molecules (CaH, CaH2, CaO, CaOH, Ca(OH)2, CaF, CaF2, CaS, CaCl, and CaCl2). B3-LYP and CCSD(T) with both the (aug-)cc-pWCVQZ and (aug-)cc-pWCVQ+dZ basis sets are found to give molecular geometries that agree well with the experimental results. The CCSD(T)(riv)/(aug-)cc-pWCVQ+dZ results are found to be the most accurate, with a mean absolute deviation from experiment of just 0.008 angstroms. Zero-point vibrational energies (ZPVEs) and thermochemical corrections are found to be relatively insensitive to the level of theory, except in the case of molecules with highly anharmonic calcium-centered bending modes (CaH2, Ca(OH)2, CaF2, CaCl2), where special procedures need to be employed in order to obtain satisfactory results. Several potential improvements to the W2C method were investigated, most of which do not produce significant changes in the heats of formation. It was observed, however, that for CaO and CaS the scalar relativistic corrections are unexpectedly large and highly basis set dependent. In these cases, Douglas-Kroll CCSD(T)/(aug-)cc-pWCV5Z calculations appear to give a converged result. The G3[CC](dir,full) and best W2C-type heats of formation are both found generally to agree well with experimental values recommended in recent critical compendia. However, in some cases (CaO, Ca(OH)2, and CaF2), they differ from one another by more than their predicted error margins. The available experimental data are not sufficiently precise to distinguish definitively between the two sets of results although, in general, when discrepancies exist the W2C heats of formation are lower in energy and tend to be in better agreement with experiment. In the case of CaO, the W2C heat of formation (20.7 kJ mol(-1)) is approximately 20 kJ mol(-1) lower than the G3[CC](dir, full) result and most of the experimental data. Extensive investigation of possible refinements of the W2C method has failed to reveal any weaknesses that could account for this discrepancy. We therefore believe that the heat of formation of CaO is likely to lie closer to the more recent direct experimental determination of 27 kJ mol(-1) than to the value of approximately 40 kJ mol(-1) recommended in recent thermochemical reviews. 相似文献
45.
Shariff E. Kabir Faruque Ahmed Mohammad R. Hassan Ayesha Sharmin Daniel T. Haworth Tasneem A. Siddiquee Kenneth I. Hardcastle 《Journal of organometallic chemistry》2008,693(16):2657-2665
Reaction of [Re2(CO)8(MeCN)2] with 1,8-bis(diphenylphosphino)naphthalene (dppn) afforded three mono-rhenium complexes fac-[Re(CO)3(κ1:η1-PPh2C10H6)(PPh2H)] (1), fac-[Re(CO)3{κ1:κ1:η1-(O)PPh2C10H6(O)PPh(C6H4)}] (2) and fac-[ReCl(CO)3(κ2-PPh2C10H6PPh2)] (3). Compounds 1-3 are formed by Re-Re bond cleavage and P-C and C-H bond activation of the dppn ligand. Each of these three complexes have three CO groups arranged in facial fashion. Compound 1 contains a chelating cyclometalated diphenylnaphthylphosphine ligand and a terminally coordinated PPh2H ligand. Compound 2 consists of an orthometalated dppn-dioxide ligand coordinated in a κ1:κ1:η1-fashion via both the oxygen atoms and ortho-carbon atom of one of the phenyl rings. Compound 3 consists of an unchanged chelating dppn ligand and a terminal Cl ligand. Treatment of [Mn2(CO)8(MeCN)2] with a slight excess of dppn in refluxing toluene at 72 °C, gave the previously reported [Mn2(CO)8(μ-PPh2)2] (4), formed by cleavage of C-P bonds, and the new compound fac-[MnCl(CO)3(κ2-PPh2C10H6PPh2)] (5), which has an unaltered chelating dppn and a terminal Cl ligand. In sharp contrast, reaction of [Mn2(CO)8(MeCN)2] with slight excess of dppn at room temperature yielded the dimanganese [Mn2(CO)9{κ1-PPh2(C10H7)}] (6) in which the diphenylnaphthylphosphine ligand, formed by facile cleavage of one of the P-C bonds, is axially coordinated to one Mn atom. Compound 6 was also obtained from the reaction of [Mn2(CO)9(MeCN)] with dppn at room temperature. The XRD structures of complexes 1-3, 5, 6 are reported. 相似文献
46.
Shariff E. Kabir Faruque Ahmed Anamika Das Mohammad R. Hassan Daniel T. Haworth Sergey V. Lindeman Tasneem A. Siddiquee Dennis W. Bennett 《Journal of organometallic chemistry》2008,693(8-9):1696-1702
Treatment of the labile compound [Re2(CO)8(MeCN)2] with 2-vinylpyridine in refluxing benzene affords exclusively the new compound [Re2(CO)8(μ-η1:η2-NC5H4CHCH2)] (1) in 39% yield in which the μ-η1:η2-vinylpyridine ligand is coordinated to one Re atom through the nitrogen and to the other Re atom via the olefinic double bond. Reaction of [Re2(CO)8(MeCN)2] with morpholine in refluxing benzene furnishes two compounds, [Re2(CO)9(η1-NC4H9O)] (2) and [Re2(CO)8(η1-NC4H9O)2] (3) in 5% and 29% yields, respectively. Reaction of [Re2(CO)8(MeCN)2] with 1-methylimidazole gives [Re2(CO)8{η1-NC3H3N(CH3)}2] (4) and the mononuclear compound fac-[ReCl(CO)3{η1-NC3H3N(CH3)}2] (5) in 18% and 26% yields, respectively. In the disubstituted compounds 2 and 4, the heterocyclic ligands occupy equatorial coordination sites. The mononuclear compound 5 consists of three CO groups, two N coordinated η1-1-methylimidazole ligands and a terminal Cl ligand. The XRD structures of complexes 1, 3 and 5 are reported. 相似文献
47.
G. Klein A. Husemann R. Brieger O. Tunmann L. Rosenthaler H. Pringsheim K. Freudenberg B. Helferich M. Bergmann B. Haworth C. S. Hudson Z. I. Kertész Ohlmüller-Spitta Wo. Olszewski A. Splittgerber E. Nolte E. Abderhalden H. Beger Else Beger R. Kolkwitz L. Utkin-Ljubowzow O. Steppuhn H. A. Krebs Th. Sabalitschka H. Haehn E. Schwab A. Hunter G. Trier Fachgruppe für Wasserchemie des Vereins Deutscher Chemiker 《Analytical and bioanalytical chemistry》1931,86(7-8):327-331
48.
Dennis W. Bennett Tasneem A. Siddiquee Daniel T. Haworth Shariff E. Kabir Md. Iqbal Hyder Syed J. Ahmed 《Journal of chemical crystallography》2004,34(6):361-370
The crystal and molecular structures of Ru3(CO)6{μ 3-OPPh2C2H(C6H4)PPhCH2PPh}-(μ 3-OPPh2)Ph (1) and Ru3(CO)6{μ-OPPh2C2H(C6H4)PPhO}(μ-PPh2)(μ-PPh2O) (2) have been determined by single crystal X-ray diffraction. Both complexes contain oxygen atoms oxidatively inserted into phosphorus–ruthenium bonds, and unique σ/π multidentate ligands formed from C $---{\text{H}}$ H and C $--$ P bond cleavage in bis(diphenylphosphino)acetylene and bis(diphenylphosphino)methane. Complex 1 crystallized in the triclinic space group ${\bar 1}$ , with lattice parameters a = 11.642(4) Å, b = 15.018(5) Å, c =16.587(5) Å, α = 2.48(3)°, β = 76.47(2)°, γ = 70.35(3)°, V = 2651.1(15) Å3, Z = 2. Complex 2 crystallized in the centered monoclinic space group, C2/c, with lattice parameters a = 34.467(4) Å, b = 14.274(2) Å, c = 23.258(3) Å, β = 5.29(1)°, V = 11394(3) Å3, Z = 8. 相似文献
49.
50.
G. Klein A. Husemann R. Brieger O. Tunmann L. Rosenthaler H. Pringsheim K. Freudenberg B. Helferich M. Bergmann B. Haworth C. S. Hudson Z. I. Kertész Ohlmüller-Spitta Wo. Olszewski Fachgruppe für Wasserchemie des Vereins Deutscher Chemiker A. Splittgerber E. Nolte E. Abderhalden H. Beger Else Beger R. Kolkwitz L. Utkin-Ljubowzow O. Steppuhn H. A. Krebs Th. Sabalitschka H. Haehn E. Schwab A. Hunter und G. Trier 《Fresenius' Journal of Analytical Chemistry》1931,86(7-8):327-331
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