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1.
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.
In this article, the preparation, X-ray powder results and vibrational properties of a new type of complex with planar dithiooxamides are discussed. In acetonitrile, Cu(I) can form complexes with the formula Cu(LH2)2X1 (X = Cl, Br) where LH2 is an N,N'-disubstituted dithiooxamide. Complexes with N,N'-dimethyldithiooxamide and N,N'-diethyldithiooxamide have been prepared. A thorough vibrational analysis with infrared and Raman techniques was performed, assisted by H/D and 63Cu/65Cu isotope substitution. The vibrational study indicates the presence of an inversion centre in the structure. This leads to the proposal of a very unusual six-coordinate structure for these compounds, with the two dithiooxamide ligands, having S-cis conformation, coordinated to the same copper and with the halogens bridged between two different copper atoms. Confirmation of this result was attempted by X-ray analysis, but although several methods were tried to obtain crystals, only powder X-ray data could be obtained, which could not give a definitive answer. Since such six-coordinate Cu(I) has never been described before, a less rigourous interpretation of the vibrational data was followed, leading to a square-pyramidal five-coordinate structure, with a rather weak bond between Cu(I) and a terminal halogen. The latter structure, with the data available up to now, seems a bit more likely, since five-coordination for Cu(I) has already been described.  相似文献   
3.
4.
Summary The synthesis of the NiII, PdII and CuII complexes of N, N-bis(aminoalkyl)oxamides (LH2) is described and structures are proposed on the basis of their physical and spectroscopic properties. With NiII and PdII only one complex is formed with general formula NiL or PdL, characterised by coordination through two deprotonated amide N-atoms and two terminal NH2 groups. With CuII it proved possible to obtain three structurally different compounds, depending on the pH, with general formulae Cu(LH2)X2, Cu2(L)X2 and CuL in which X=Cl, Br or NO3. The structure of [Cu2(C8O2N4H16](NO3)2 was solved by means ofx-ray diffraction; Mr=451.33, monoclinic, space group P21/n, a=9.503(4), b=7.614(1), c=10.407(3) Å, =98.43(3)°, V=744.3(7)Å3, Z=2, Dx=1.202 g cm–3, =1.33 cm–1, (MoK)=0.71073 Å, F(000)=520, room temperature, R=0.043, wR=0.047 for 1080 observed [I>-3(I)] not systematically absent reflections out of 1423 measurements and 137 variables. The compound has a conformational chair/boat disorder with 82% in the more stable chair form.  相似文献   
5.
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   
6.
Summary The new complexes K2[ML2]·2H2O (M=Ni, Cu), K2[PdL2]·H2O, K2[CuL2(H2O)2]·H2O, [Ni(LH2)Cl2]x ·xH2O and [Ni(LH2)Br2]x·1,5xH2O, where LH2= oxalyldihydrazide, have been prepared. Emphasis has been put on determining the conditions for the synthesis of both deprotonated and non-deprotonated NiII complexes. They were characterized by analyses, conductivity measurements, thermogravimetry, magnetic susceptibility and spectroscopic methods like i.r. and far-i.r., diffuse reflectance u.v. vis, and e.s.r. Monomeric square planar and distorted octahedral structures were found for the deprotonated complexes in the solid state while the non-deprotonated NiII complexes appeared to be pseudo-tetrahedral polymers. The doubly deprotonated L2-ion exhibits a bidentate N(amide), N(amide)-coordination, while the neutral LH2 molecule behaves as a N(amino), N(amino)-bidentate ligand forming polymeric structures. Vibrational analysis of the complexes was carried out, using hydrogen and metal isotopic substitution.  相似文献   
7.
Dithiomalonamide [H2A, CH2(CSNH2)2] and 2,2-dimethyldithiomalonamide [H2B, C(CH3)2(CSNH2)2] can act as bidentate ligands and form stable, cationic 1∶2 complexes with general formula M2(H2L)2X2 [M=Ni2+, Pd2+, Pt2+;X=C1, Br, I; H2L=H2A, H2B] in strong acidic medium. An elaborate thermal study is presented, based on results from elemental analyses and vibrational studies (IR and Raman spectroscopy). The H2A complexes start to decompose by releasing two HX molecules whereafter a stable intermediate M(HA)2 is formed. The H2B complexes degrade in a different way; the metal-sulphur bond is broken and the ligand is expelled as a whole. Influences of the metal ion and of the halogenide counterions are investigated.  相似文献   
8.
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   
9.
Ramos A  San Emeterio JL  Sanz PT 《Ultrasonics》2000,38(1-8):553-558
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   
10.
Planar Pd(LH)2 complexes (LH2 = H2N C S C S N H2, CH3HNCSCSNHCH3) form mixed polymeric complexes with Ni(II), Cu(II), Zn(II) and Cd(II) in alcalic media, where the planar Pd(LH)2 complexes act as tetradentates with N-coordination. The electronic spectra and thermal behaviour are discussed, a thorough investigation of the i.r. spectra is presented and special attention has been given to the H/D, CH3/CD3 and 58Ni/62Ni, 63Cu/65Cu and 64Zn/68Zn isotopic shifts.  相似文献   
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