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151.
Huynh MH Lasker JM Wetzler M Mort B Szczepura LF Witham LM Cintron JM Marschilok AC Ackerman LJ Castellano RK Jameson DL Churchill MR Jircitano AJ Takeuchi KJ 《Journal of the American Chemical Society》2001,123(36):8780-8784
The influence of two different di(1-pyrazolyl)alkane ligands on the rate constant of aqua ligand substitution of ruthenium(II) complexes with the formula [Ru(H2O)(L2)(tpmm)]2+ (L2 = di(1-pyrazolyl)methane (DPMet) or 2,2-di(1-pyrazolyl)propane (DPPro)) was investigated. A 9.4 x 10(5)-fold increase in the rate constant of ligand substitution at pH = 6.86 was observed when DPMet was replaced with DPPro. This remarkable increase was unexpected, considering that these bidentate ligands appear quite similar. To help lend insight into this dramatic spectator ligand effect, the activation parameters for the ligand substitution reactions were determined, and single-crystal X-ray data were collected on the structurally analogous (chloro)ruthenium(II) complexes, [Ru(Cl)(L2)(tpmm)]+. These results are discussed in the context of a heteroscorpionate effect exerted by the DPPro ligand. 相似文献
152.
Melvyn Rowen Churchill Charles H. Lake Carol A. Bessel My Hang Vo Huynh Jacinta McCourt Kenneth J. Takeuchi 《Journal of chemical crystallography》1996,26(4):267-275
The complexcis-[Ru{4,4-(t-Bu)2bpy}2(PPh3)Cl+][ClO
4
–
·0.5(toluene)·0.5(MeCN), where 4,4-(t-Bu)2bpy=4,4-di(t-butyl)-2,2-bipyridyl crystallizes with an ordered racemic mixture of the chiral cations in the centrosymmetric triclinic space group
(No. 2). The structure was refined toR=4.42% for those 6426 reflections with 20=5–50o and |F
o|>6(F). Ruthenium ligand distances are Ru–Cl=2.423(2)Å, Ru–PPh3=2.346(2)Å and Ru–N=2.056(4)–2.098(4)Å. Both the Ru(II)-containing cation and the perchlorate anion are ordered, but the toluene and acetonitrile exhibit an interesting type of scrambled disorder about the inversion center atx=1,y=1/2,z=0. 相似文献
153.
Jennifer L. White Joseph M. Tanski David G. Churchill Arnold L. Rheingold Daniel Rabinovich 《Journal of chemical crystallography》2003,33(5-6):437-445
2-Mercapto-1-tert-butylimidazole (HmimtBu) and its Group 12 metal complexes (HmimtBu)2 MBr2 (M = Zn, Cd, Hg) have been readily prepared and structurally characterized. Whereas the former displays a dimeric structure in the solid state with two S H–N interactions linking each pair of molecules, the four-coordinate complexes exhibit distorted tetrahedral geometries with the S–M–S angles in the range 103.2–135.2. The average M–Br bond lengths are 2.401, 2.567, and 2.688 Å for M = Zn, Cd, and Hg, respectively, and the corresponding average M–S bond distances are 2.350, 2.540, and 2.467 Å. The average C–S bond length for all the complexes (1.72 Å) is only ca. 0.02 Å longer than the corresponding value in the free ligand. HmimtBu is orthorhombic, space group Pbca, a = 10.1571(5) Å, b = 9.7906(5) Å, c = 17.6616(9) Å, V = 1756.34(15) Å3, Z = 8; (HmimtBu)2ZnBr2 is monoclinic, space group C2/c, a = 17.187(3) Å, b = 8.9908(17) Å, c = 15.560(3) Å, = 117.206(3), V = 2138.3(7) Å3, Z = 4; (HmimtBu)2CdBr2 is triclinic, space group P
, a = 7.4625(6) Å, b = 9.6149(9) Å, c = 31.020(3) Å, = 93.485(2), = 94.579(2), = 103.872(2), V = 2146.6(3) Å3, Z = 4; (HmimtBu)2HgBr2 is monoclinic, space group P21/c, a = 6.8908(6) Å, b = 10.2397(9) Å, c = 29.859(3) Å, = 94.364(2), V = 2100.7(3) Å3, Z = 4. 相似文献
154.
Melvyn Rowen Churchill Lynn M. Krajkowski My Hang Vo Huynh Kenneth J. Takeuchi 《Journal of chemical crystallography》1996,26(1):67-73
The complexcis-[Ru(bpy)2{PPh(o-tolyl)2}Cl+][ClO4
–] crystallized from a solution in dichloromethane as the dichloromethane-water solvate. The structure was refined toR=4.5% for those 2433 reflections with |F
o|>6(|F
o|). The octahedral Ru(II) cation is associated with metal-ligand distances as follows: Ru–Cl=2.434(3)Å, Ru-PPh(o-tol)2=2.382(2)Å, and Ru–N=2.037(7)–2.088(7)Å. The structure is stabilized by a hydrogen-bonded CH2Cl2...ClO4
–...H2O channel which incorporates adventitious water of crystallization. 相似文献
155.
Melvyn Rowen Churchill Lynn M. Krajkowski Lisa F. Szczepura Kenneth J. Takeuchi 《Journal of chemical crystallography》1996,26(12):853-859
The complexmer,trans-[Ru(NO2)(trpy)(PPh3)
2
+
][PF
6
–
] crystallizes in the centrosymmetric monoclinic space groupP21/n withZ=4; the ruthenium atom lies close toy=1/4 and all data withh+l=2n+1 are systematically weak. The trpy ligand is not strictly planar, but has a dish-like geometry. The nitro ligand is rotated from the plane of the Ru(trpy) moiety, the N3Ru/NO2 interplanar angle being 32.5o. Ruthenium-ligand distances are: Ru–PPh3=2.418(4) Å and 2.429(4) Å, Ru–NO2=2.063(12) Å, Ru–N(trpy, outer)=2.100(12) Å and 2.116(12) Å and Ru–N(trpy, central)=2.004(11) Å. 相似文献
156.
Melvyn Rowen Churchill Charles H. Lake Cynthia A. Miller Jim D. Atwood 《Journal of chemical crystallography》1994,24(8):557-560
The title compound crystallizes in the centrosymmetric triclinic space group
(C
1
l
; No.2) witha=9.9143(10) Å,b=10.2616(11) Å,c=10.7715(10) Å, =113.887(8)°, =109.197(8)°, =90.699(9)°,V=932.78(17) Å3 andZ=1. A total of 4869 data were collected and merged to a set of 2450 independent reflections; the structure was solved and refined toR=1.42% andwR=1.94%. The molecule lies on a site of
symmetry and is disordered, with obvious scrambling of carbonyl and chloride ligands. Resulting bond lengths include Ir–P=2.339(1) Å, Ir–Cl=2.398(4) Å and Ir–CO=1.808(15) Å. 相似文献
157.
Melvyn Rowen Churchill Lynn M. Krajkowski My Hang Vo Huynh Kenneth J. Takeuchi 《Journal of chemical crystallography》1991,27(10):589-597
The complexcis-[Ru(bpy)2(PMe3)Cl+][ClO4
−] crystallizes in space group P21/c andcis-[Ru(bpy)2{PMe2(o-tol)]Cl+][ClO4
−] crystallizes in space group
; each is present as a racemate and neither structure suffers from disorder. The Ru−PMe2(o-tol) bond length of 2.324(2)? is slightly longer than the simple Ru−PMe3 bond length of 2.310(2) ?. 相似文献
158.
Crystal structure of hexakis(tetrahydrofuran)sodium hexacarbonylvanadate(−I), [Na(THF)6
+][V(CO)6
−]
The title compound crystallizes in the space group
with unit cell parameters (hexagonal setting)a=14.922(5)Å,c=14.379(9)Å,V=2773(3)Å3 andZ=3. The cation and the anion each lie on a site of
(S6) symmetry. Interatomic distances include Na–O(THF)=2.40(1) Å and V–C(CO)=1.91(2) Å. 相似文献
159.
Melvyn Rowen Churchill David George Churchill Gulzar Ahmed Huw M.L. Davies 《Journal of chemical crystallography》1999,29(6):713-717
The compound under investigation crystallizes in the noncentrosymmetric monoclinic space group P21 with a = 9.1798(23), b = 6.6606(18), c = 17.6591(41) Å, = 94.342(20)° and Z = 2. The C20H30O6Si molecule contains three chiral centers (one of which is of known configuration, based upon an (R)-pantolactone auxiliary group). We have determined the absolute configuration of this species (via the anomalous dispersion of Si relative to C and O) and show that it is consistent with the known configuration of the (R)-pantolactone moiety 相似文献