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1.
Combining Surface Organometallic Chemistry with rigorous olefin purification protocol allows evaluating and comparing the intrinsic activities of Mo and W olefin metathesis catalysts towards different types of olefin substrates. While well‐defined silica‐supported Mo and W imido‐alkylidenes show very similar activities in metathesis of internal olefins, Mo catalysts systematically outperform their W analogs in metathesis of terminal olefins, consistent with the formation of stable unsubstituted W metallacyclobutanes in the presence of ethylene. However, Mo catalysts are more prone to induce olefin isomerization, in particular when ethylene is present, probably because of their propensity to undergo more easily reduction processes.  相似文献   

2.
The results of structural investigations of vanadium, molybdenum, and tungsten polyoxoanions (PA) by 17O, 51V, 95Mo, 183W, and heteroatom NMR are generalized in this review. NMR spectroscopy possibilities to determine the structure of PA are discussed. NMR data on PA of different structures compositions nuclei are demonstrated.  相似文献   

3.
Li H  Yang HK  Moon BK  Choi BC  Jeong JH  Jang K  Lee HS  Yi SS 《Inorganic chemistry》2011,50(24):12522-12530
Lu(6)WO(12) and Lu(6)MoO(12) doped with Eu(3+) ions have been prepared by using a citrate complexation route, followed by calcination at different temperatures. The morphology, structure, and optical and photoluminescence properties of the compounds were studied as a function of calcination temperature. Both compositions undergo transitions from a cubic to a hexagonal phase when the calcination temperature increases. All the compositions have strong absorption of near-UV light and show intense red luminescence under a near-UV excitation, which is related to the transfer of energy from the host lattices to dopant Eu(3+) ions. Density functional theory calculations have also been performed. The calculation reveals that hexagonal Lu(6)WO(12) and Lu(6)MoO(12) are indirect bandgap materials, and the near-UV excitations are due to the electronic transitions from the O-2p orbitals to W-5d and Mo-4d orbitals, respectively. The lattice parameters and bandgap energies of hexagonal Lu(6)WO(12) and Lu(6)MoO(12) were determined.  相似文献   

4.
State of the art CASSCF and CASPT2 calculations have been performed to elucidate the nature of the electronic transitions observed in the experimental spectrum of the octacyanomolybdate(V) cation. Assuming a triangular dodecahedral structure for this complex gives a convincing agreement between theory and experiment. All absorption bands are assigned to low-lying charge-transfer transitions involving excitations from ligand orbitals to 4dx2-y2. The calculated molecular orbitals reveal weak pi interactions between the metal and ligand orbitals, compared to much stronger sigma interactions. This calculated electronic structure substantiates the previous hypothesis concerning the giant spin ground states of magnetic clusters and networks containing Mo(CN)8(3-) as a constituent part.  相似文献   

5.
Raman and far-i.r. measurements are reported for salts of the ions [MoCl6]n− (n = 1, 2, 3) and [WCl6]n− (n = 1, 2). The frequencies v1, v3, v4, and v5 for these ions, many of which have not been measured previously, were thus mostly identified, but v2 was not observed for any of these ions.  相似文献   

6.
Some aspects of the interaction of (NH4)42[Mo 72 VI Mo 60 V O372(H3CCOO)30(H2O)72] · 30H3CCOONH4 · 250H2O (polyoxometalate Mo132) with a water-soluble nonionic polymer (poly(vinyl alcohol) or related poly(vinylpyrrolidone)) were studied in aqueous solutions and in films. A set of methods was used: spectrophotometry, EPR spectroscopy, visual microscopy, X-ray powder diffraction, scanning probe microscopy, and potentiometry. The complex-formation features of the system were revealed. The miscibility of the components and their influence on crystallization phenomena were considered. The effect of UV and X-rays on poly(vinyl alcohol) + polyoxometalate films was studied. Poly(vinyl alcohol) stabilizes the polymer. Mutual radiation and thermal stabilization of the polymer and polyoxometalate was discovered. The utility of ion-sensitive electrodes for Mo132 determination in solution was demonstrated.  相似文献   

7.
8.
Under suitable conditions liquids crystallize. In this article, we establish with examples from the literature and our own works that the soft-matter state of oxometalates or soft-oxometalates (SOMs) is such a liquid. We further demonstrate that POM crystallization can be considered as a phase transition from SOMs. The review concludes with implications of such a point of view in futuristic materials design.  相似文献   

9.
The usefulness of qualitative and quantitative theoretical approaches in solid state chemistry is discussed by considering three different types of problems: (a) the distribution of boron and carbon atoms in MB2C2 (M=Ca, La, etc.) phases, (b) the band structure and Fermi surface of low-dimensional transition metal oxides and bronzes, and (c) the correlation between the crystal and electronic structure of the ternary nitride Ca2AuN.  相似文献   

10.
The ground-state electronic structure of W3S82− has been calculated using the relativistic SCF-MS-X method. The results confirm a formal oxidation state of +2 for the central tungsten atom and a + 6 oxidation state for the terminal ones. A W---|W σ bond is detected within the 7a1g molecular orbital leading to a W---|W bond order of 1/2. The energy order of the X MOs of ligand field interest, localized on the central metal ion, is explained based on the simple angular overlap approach taking into consideration the W---|W interactions.  相似文献   

11.
陈忠  蔡淑惠 《结构化学》1997,16(2):153-158
对含有[MS4]2-(M=Mo,W)单元的一系列钼(钨)-钼-硫簇合物进行了95MoNMR研究,定性分析了95Mo化学位移随金属原子配位数、配位金属种类和配位金属配体改变而变化的规律。结果表明,随着[MoS4]2-配位金属原子数的增加,[MoS4]2-上Mo的化学位移逐渐向高场移动,这可归因于低氧化态MO0上的电子通过硫桥离域到高氧化态的Mo上。为了解析Mo0上化学位移的实验结果,采用MM+力场对[(OC)4MOS2MoS2]2-和[{(OC)4Mo}MoS4]2-的晶体结构进行几何优化,使之更接近于溶液中的结构,然后利用Fenske-Hall方法计算Mo原子上的净电荷分布,计算结果较好地好择了Mo和Mo0化学位移的变化趋势。  相似文献   

12.
Cyclic voltammetry (CV) measurements on (eta(2)-C(60))M(CO)(5) complexes (M = Cr, Mo, W) in dichloromethane show three [60]fullerene-centered and reversible reduction/oxidation waves. The E(1/2) values of these waves are shifted to positive values relative to the corresponding values of the uncoordinated [60]fullerene in the same solvent. A Jahn-Teller type distortion of the spherical surface of [60]fullerene promoted by [60]fullerene-metal pi-backbonding may explain the observed positive shifts. Lewis bases (L = piperidine and triphenyl phosphine) displace [60]fullerene from (eta(2)-C(60))M(CO)(5) complexes. Analysis of the activation parameters for the metal-[60]fullerene dissociation, the metal-[60]fullerene bond enthalpies (from DFT computations), and metal-solvent (benzene) bond enthalpies (from DFT computations) suggests appreciable solvent contribution to the transition state leading to formation of the intermediate species solvent-M(CO)(5). Appreciable transition state stabilization due to solvation of the intermediate species is inferred for M = Mo and W. For M = Cr, stabilization of the intermediate species due to solvation is not accompanied by the corresponding transition state stabilization.  相似文献   

13.
The structural stability and electronic properties of the recently characterized three-dimensional (3D) cuboid-shaped C(60) polymer are studied using periodic ab initio density functional methods. It is shown that the experimentally observed structure is metastable and not fully relaxed from the high pressure state. A second polymorph, which is more stable than the experimental structure, is identified from the calculations. This new structure differs from the observed structure in the number of fourfold-coordinated atoms per C(60) molecule. Both structures are found to be metallic with bulk moduli only about one-third that of diamond. The cuboidal C(60) is not the long sought after superhard 3D carbon polymer; however, the two polymorphs studied here reveal unusual electronic band structures that might suggest interesting electronic properties.  相似文献   

14.
以合成为目的,研究了Mo_3S_4(dtp)_4(H_2O)(Ⅰ)、Mo_3OS_3(dtp)_4(H_2O)(Ⅱ)、W_2S_4(dtp)_2(Ⅲ)等为主的簇合物的反应及其产物。包括配基置换反应,加硫和脱硫反应,簇合反应,簇解和局部氧化反应。讨论了反应物的结构和试剂两个方面对反应的影响,由此总结了若干反应规律。本文还以Mo_4S_4(OAc)_2(dtp)_4和Mo_3XS_6(dtp)_3Y(X=S,O;Y=I,Cl)为例,阐述了设计合成的基本思路。  相似文献   

15.
16.
Two hybrid assemblies (3 and 4) with two kind of nanoscaled cluster units, the spherical [Co(24)(TC4A)(6)(MO(4))(8)Cl(6)](2+) cation (1 and 2) and Keggin-type [PM(12)O(40)](3-) anion (M = Mo (1/3), W (2/4)), were solvothermally prepared and characterized, in which the spherical units are constructed by six Co(4)-p-tert-butylthiacalix[4]arene (Co(4)-TC4A) SBUs linked by eight MO(4) tetrahedrons and present the highest nuclearity bimetallic clusters capped by cailxarenes.  相似文献   

17.
The preparation of 2,6-azulenedicarboxylic acid (I) from its diester, 2-CO(2)(t)Bu-6-CO(2)-C(10)H(6) (II), is reported together with the crystal and molecular structure of the ester, II. From the reactions between the dicarboxylic acid I and the MM quadruply bonded complexes M(2)(O(2)C(t)Bu)(4), where M = Mo or W, the azulenedicarboxylate bridged complexes [M(2)(O(2)C(t)Bu)(3)](2)(mu-2,6-(CO(2))(2)-C(10)H(6)) have been isolated, III (M = Mo) and IV (M = W). The latter compounds provide examples of electronically coupled M(2) centers via a polar bridge. The compounds show intense electronic absorptions due to metal-to-bridge charge transfer. This occurs in the visible region of the spectrum for III (M = Mo) but in the near-IR for IV (M = W). One electron oxidation with Ag(+)PF(6)(-) in THF generates the radical cations III(+) and IV(+). By both UV-vis-NIR and EPR spectroscopy the molybdenum ion III(+) is shown to be valence trapped or Class II on the Robin and Day classification scheme. Electrochemical, UV-vis-NIR, and EPR spectroscopic data indicate that, in the tungsten complex ion IV(+), the single electron is delocalized over the two W(2) centers that are separated by a distance of ca. 13.6 A. Furthermore, from the hyperfine coupling to (183)W (I = (1)/(2)), the singly occupied highest molecular orbital is seen to be polarized toward one W(2) center in relationship to the other. Electronic structure calculations employing density functional theory indicate that the HOMO in compounds III and IV is an admixture of the two M(2) delta orbitals that is largely centered on the M(2) unit having proximity to the C(5) ring of the azulenedicarboxylate bridge. The energy of the highest occupied orbital of the bridge lies very close in energy to the M(2) delta orbitals. However, this orbital does not participate in electronic coupling by a hole transfer superexchange mechanism, and the electronic coupling in the radical cations of III and IV occurs by electron transfer through the bridge pi system.  相似文献   

18.
Russian Journal of Physical Chemistry A - The possibility of changing the hydrophilic (polar) surfaces of toroid nanocluster polyoxomolibdates to hydrophobic (nonpolar) surfaces via the...  相似文献   

19.
20.
Na(1.5)Ag(1.5)MoO(3)F(3) and Na(1.5)Ag(1.5)WO(3)F(3) have been synthesized by solid state reactions and structurally characterized using synchrotron X-ray and neutron powder diffraction. Unlike the vast majority of salts containing [MO(3)F(3)](3-) anions (M = Mo, W) the oxyfluoride groups in Na(1.5)Ag(1.5)MoO(3)F(3) and Na(1.5)Ag(1.5)WO(3)F(3) are orientationally ordered, so that the Na(+) ions are coordinated by fluorine and the Ag(+) ions by oxygen. The resulting structure type, which has not previously been reported, is related to the LiNbO(3) structure, but the combination of Na/Ag ordering and orientational ordering of the [MO(3)F(3)](3-) anions produces a supercell that doubles the c-axis and changes the space group symmetry from R3 to R3. The use of hard (Na(+)) and soft (Ag(+)) cations to direct the orientational ordering of polar oxyfluoride building units provides a new approach to the design of polar materials.  相似文献   

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