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本实验测定了2.4-二酮-5-咪唑烷基尿的~(15)N和~(13)C NMR谱并确认了谱线归属。根据化学位移及其在脱质子化过程中的变化,讨论了化合物的互变异构平衡及立体构型的转化问题。结果表明,在溶液中此化合物以酮式结构(A)为主要构型。 相似文献
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在脉冲傅里叶变换~(13)C核磁共振研究中,~(13)C偏共振谱,因为它谱线的多重性直接与碳原子的类型有关,从残余偶合常数的大小又可以定性地了解碳原子与分子中电负性基因之间的相对位置,所以与宽带质子去偶~(13)C谱一起成了确定谱线归属和研究分子结构最常用的~(13)C图谱。然而,正是因为在偏共振谱中~(13)C信号以多重峰形式出现,信噪比随之下降,使得实 相似文献
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XCu(PP?h_?)_3,(X为卤素、硼氢阴离子等)是一类稳定的亚铜络合物,对一些有机反应和聚合反应有催化作用,曾用于多种成像过程,因而吸引人们对这一类化合物的结构和性质进行了广泛的研究。Lippard等测定了这类化合物在溶液中的表观分子量表明,在溶液中这类化台物的配体可以离解,并与络合物形成动态平衡。本文用 FX-90Q NMR 谱仪研究了四种络合物(PPh_3)_3CuX(X=Cl~-、Br~-、I~-和CN~-)在氯仿溶液中的~(32)PNMR谱及加入不同浓度的PPh_3对其~(35)P 相似文献
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本文报导了六个二氢十氟环己烷异构体的~(13)C NMR的化学位移和偶合常数,指定了谱峰的归属,并对数据进行了讨论。含氟化合物~(13)C NMR谱中谱峰的归属主要通过预先确定~(19)F谱的谱峰归属,然后通过作~(19)F的选择性去偶的~(13)C NMR谱来定出~(13)C谱谱峰的归属。 相似文献
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冠醚化合物以其特殊的配合选择性受到化学工作者的重视,其结构与性能的研究已广泛引起人们的兴趣。本文对新合成的七种冠醚化合物测定了~1H和~(13)C NMR谱,并利用文献值和本组化合物的系列性对谱线进行了归属和讨论。实验部分七种冠醚化合物均由武汉大学化学系合成,其结构式见表1。样品在5mm样品管中以0.5ml CDCI_3(北京化工厂产品)为溶剂配成浓度约为0.5M的溶液。用美国Varian公司XL-200谱仪记谱。探头温度20.0±0.1℃,样品管旋转速度25±5Hz,以氘代氯仿为内锁场信号。 相似文献
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Although Si or Ge is not known to form empty cage clusters such as the fullerenes, we recently found a unique 12-atom icosahedral tin cluster, Sn12 2- (stannaspherene). Here we report photoelectron spectroscopy and theoretical evidence that Pb12 2- is also a highly stable icosahedral cage cluster and bonded by four delocalized radial pi bonds and nine delocalized on-sphere sigma bonds from the 6p orbitals of the Pb atoms. Following Sn12 2-, we coin a name, plumbaspherene, for the highly stable and nearly spherical Pb12 2- cluster, which is expected to be stable in solution and the solid state. Plumbaspherene has a diameter of approximately 6.3 A with an empty interior volume large enough to host most transition metal atoms, affording a new class of endohedral clusters. 相似文献
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The electronic structures and stabilities of pure M(12)- and M(12)(2-) were systematically investigated within density functional theory. The nucleus-independent chemical shifts (NICSs) of I(h) Sn(12)(2-) and Pb(12)(2-) are -5.0 and -20.7 ppm, respectively, based on B3LYP/aug-cc-pVDZ-PP predictions, whereas the NICS of Sn(12)(2-) is predicted to be 1.1 ppm by B3LYP/LanL2DZ. A startling conclusion is that the NICS4d of Sn(12)(2-) and NICS(5d) of Pb(12)(2-) are -5.0 and -7.5 ppm, respectively, suggesting the significant contribution of the inner d orbitals to the total NICS values. This provides the first quantitative evidence for the existence of "d-orbital aromaticity" in Sn- and Pb-based clusters with three-dimensional structures. The d orbitals also contribute to the total NICSs of the K-coordinated clusters. The NICS predictions suggest that larger basis sets including d-orbitals are needed to analyze the aromaticity of some main-group-metal-based clusters (e.g., Sn- and Pb-based clusters) to obtain accurate predictions. 相似文献
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通过比较激光烧蚀E1/E2 (代表Ge/Sn, Ge/Pb和Sn/Pb) 和Co/E (E为Ge、Sn、Pb)混合样品形成的二元团簇负离子飞行时间质谱分布和谱峰的相对强度及形成的幻数团簇离子峰,发现E1/E2二元团簇离子中原子量大的锗分族元素在团簇离子中占主要组分,而原子量小的元素则少量掺杂,其组成和分布特点说明其结构和性质与纯E团簇离子相似,可能的结构为该类负离子团簇所有原子都在笼结构的骨架上;对于二元团簇离子GeSn9-、GePb9-和SnPb9-其结构可能是双帽反四棱柱构型,只是每个原子均为骨架的一部分.而对激光烧蚀过渡金属钴与锗分族元素的混合物的研究发现,反应形成了丰富的Co/E二元合金团簇负离子,分析发现该类簇离子为钴内包覆于E(锗分族元素)笼状结构.幻数离子CoGe10-、CoSn10-和CoPb10-可能具有双帽四角反棱柱结构,而CoPb12-可能具有二十面体构型,钴原子均为笼状结构的中心. 相似文献
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Elusive for over 100 years, deltahedral Zintl ions of silicon are finally synthesized and structurally characterized. The two clusters reported here, Si93- and Si52-, are analogous to known clusters of the heavier members of this group: Ge, Sn, and Pb. 相似文献
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The ligand-free [Ni2Sn17]4- ion comprises two [Ni@Sn9]2- clusters that share a common vertex. The cluster sequentially loses Sn atoms in the gas phase and shows global exchange of all Sn atoms on the NMR time scale in solution at 60 degrees C. At lower temperatures, the fluxionality is localized to the ends of the cluster and does not involve the central 8-coordinate Sn5 atom. 相似文献
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利用从头算MP2方法和密度泛函理论B3LYP和B3PW91方法, 研究了杂硼原子簇XB6+ (X=C, Si, Ge, Sn, Pb)的结构、稳定性及化学键合情况. 对C, Si, Ge, B使用6-311+G(d)基组, 对Sn和Pb使用LANL2DZ赝势基组. 研究结果表明, 具有Cs对称性的假平面XB6+ (X=C, Si, Ge, Sn, Pb)结构是势能面上的全域极小点, 其稳定性要高于C6v对称性的锥形结构和C2对称性的假锥形结构. 在B3LYP水平上, 对这些异构体的势能面的极小点进行了自然键轨道(NBO)的分析; 对最稳定构型的最高占据分子轨道(HOMO)和最低空轨道(LUMO)能级差、分子轨道(MO)和核独立化学位移(NICS)进行了计算和讨论. 分析了杂原子和硼原子间、相邻硼原子间的键合情况, 讨论了最稳定构型的芳香性质. 相似文献
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Kocak FS Zavalij P Eichhorn B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(17):4858-4863
Pyridine/ethylenediamine solutions of [Sn(9)SnCy(3)](3-) (1) react with [Pd(PPh(3))(4)] to give new clusters [Pd@Sn(9)SnCy(3)](3-) (2) and [Pd@Sn(9)PdSnCy(3)](3-) (3), depending on stoichiometry. These compounds are formed sequentially and are the first transition metal derivates of exo-substituted Zintl clusters. Oxidative insertion of a Pd atom into the Pd@Sn(9)-SnCy(3) bond of 2 to form 3 represents a new reaction type for Zintl cluster compounds. The conversion Sn(9)(4-)→1→2→3 is a rare case in which charge and mass are conserved in a series of Zintl clusters. Complexes 1, 2, and 3 are all highly fluxional in solution. In all three clusters, the nine Sn vertices are in rapid exchange on the NMR timescale. In 1 and 2, the exo-SnCy(3) substituent also scrambles intramolecularly around the outside of the clusters. In 3, the SnCy(3) group remains attached to the vertex Pd atom. The disparate reactions with the other RSn(9)(3-) ions are discussed. 相似文献
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Silicon (Si), germanium (Ge), tin (Sn), and lead (Pb) clusters mixed with a group-4 transition metal atom [M = titanium (Ti), zirconium (Zr), and hafnium (Hf)] were generated by a dual-laser vaporization method, and their properties were analyzed by means of time-of-flight mass spectroscopy and anion photoelectron spectroscopy together with theoretical calculations. In the mass spectra, mixed neutral clusters of MSi(16), MGe(16), and MSn(16) were produced specifically, but the yield of MPb(16) was low. The anion photoelectron spectra revealed that MSi(16), MGe(16), and MSn(16) neutrals have large highest occupied molecular orbital-lowest unoccupied molecular orbital gaps of 1.5-1.9 eV compared to those of MPb(16) (0.8-0.9 eV), implying that MSi(16), MGe(16), and MSn(16) are evidently electronically stable clusters. Cage aromaticity appears to be an important determinant of the electronic stability of these clusters: Calculations of nucleus-independent chemical shifts (NICSs) show that Si(16)(4-), Ge(16)(4-), and Sn(16)(4-) have aromatic characters with negative NICS values, while Pb(16)(4-) has an antiaromatic character with a positive NICS value. 相似文献
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Using the first-principles method with the generalized gradient approximation, the authors have studied the structural and electronic properties of Al(12)X(+) (X=C, Si, Ge, Sn, and Pb) clusters in detail. The ground state of Al(12)C(+) is a low symmetry C(s) structure instead of an icosahedron. However, the Si, Ge, Sn, and Pb atom doped cationic clusters favor icosahedral structures. The ground states for Al(12)Si(+) and Al(12)Ge(+) are icosahedra, while the C(5nu) structures optimized from an icosahedron with a vertex capped by a tetravalent atom have the highest binding energy for Al(12)Sn(+) and Al(12)Pb(+) clusters. The I(h) structure and the C(5nu) structure are almost degenerate for Al(12)Ge(+), whose binding energy difference is only 0.03 eV. The electronic properties are altered much by removing an electron from the neutral cluster. The binding strength of a valence electron is enhanced, while the binding energy of the cluster is reduced much. Due to the open electronic shell, the band gaps between the highest occupied molecular orbital and the lowest unoccupied molecular orbital are approximately 0.3 eV for the studied cationic clusters. 相似文献
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Kesanli B Fettinger J Eichhorn B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(24):5277-5285
The closo-[Sn9M(CO)3]4-ions where M = Cr (1), Mo (2), W (3) were prepared from [LM(CO)3] precursors (L=mesitylene, cycloheptatriene), K4Sn9. and 2,2,2-cryptand in ethylenediamine/toluene solvent mixtures. The [K(2,2,2-cryptand)]+ salts are very air and moisture sensitive and have been characterized by IR, 119Sn, and 13C NMR spectroscopy and single-crystal X-ray diffraction studies. Complexes 1-3 form bicapped square-antiprismatic 10-vertex 22-electron closo structures in which the [M(CO)3] units occupy cluster vertices. For 1 and 2, the clusters have C4. symmetry in the solid state in which the [M(CO)A] fragments occupy capping positions with Sn9(4-) ions that are bound to the metal in an 4 fashion. For 3, the [M(CO)3] fragment occupies a position in the square plane with an eta/5-Sn9(4-) ion and C(s) point symmetry. For 1-3, a dynamic equilibrium exists between the eta4 and eta5 structures yielding three 119Sn NMR signals that reflect the three chemically distinct Sn environments of the higher symmetry C(4v) structure. The 119Sn NMR chemical shifts and coupling constants show solvent and temperature dependencies due to the equilibrium process. A triangular-face rotation mechanism is proposed to describe the dynamic behavior. 相似文献