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161.
Noorjahan Begum Amarash C. Ghosh Shariff E. Kabir Md. Arzu Miah G.M. Golzar Hossain 《Polyhedron》2005,24(18):3074-3081
Four triosmium carbonyl clusters bearing terminal pyrazines, bridging hydroxy and methoxycarbonyl ligands of general formula [Os3(CO)9(μ-OH)(μ-OMeCO)L] (1, L = pyrazine; 2, L = 2-methylpyrazine; 3, L = 2,3-dimethylpyrazine; 4, L = 2,3,5-trimethylpyrazine) were synthesized by the reactions of [Os3(CO)12] with the corresponding pyrazine derivatives and water in the presence of a methanolic solution of Me3NO in moderate yields. Compounds [Os3(CO)9(μ-OH)(μ-OMeCO)L] react with a series of two electron donor ligands, L′ at ambient temperature to give [Os3(CO)9(μ-OH)(μ-OMeCO)L′] (5, L′ = PPh3; 6, L′ = P(OMe)3; 7, L′ = tBuNC; 8, L′ = C5H5N) in good yields by the displacement of the pyrazine ligands. This implies that the pyrazine ligands in 1–4 are relatively labile. Compounds 2, 3, 4, and 8 were characterized by single crystal X-ray diffraction analyses. All the four compounds possess two metal–metal bonds and a non-bonded separation of two osmium atoms defined by Os(1)Os(3), which are simultaneously bridged by OH and MeOCO ligands and a heterocyclic ligand is terminally coordinated to one of the two non-bonded osmium atoms. 相似文献
162.
Nanocrystalline TiO2 (sample S1) was prepared from a titanium oxo cluster (Ti7O4(OEt)20) precursor via a sol-gel route. This photocatalyst showed a higher photocatalytic activity than the TiO2 (sample S2) obtained from titanium tetraisopropoxide. The samples were characterized by thermal analysis (TGA/DSC), X-ray diffraction, micro-Raman spectroscopy, transmission electron microscopy, N2 adsorption (BET surface area), infrared absorption spectroscopy (FT-IR) and X-ray photoelectron spectroscopy. The characterization results show that both samples are anatase nanocrystals with particle sizes of about 12 nm, but the more photocatalytically active sample S1 has more surface hydroxyl groups and larger surface area and pore volume than sample S2. 相似文献
163.
A new family of quaternary carbon and nitrogen containing Rare Earth (RE: Sc, Y, Ho, Er, Tm and Lu) borides: REB15.5CN, has been synthesized and structurally characterized by powder X-ray diffraction data. They are all isotypic with Sc1−xB15.5CN whose structure was solved based on single-crystal X-ray data and HRTEM investigations. The structure refinement converged at a R(F2) value of 0.044 for 364 reflections. The new structure type of Sc1−xB15.5CN is composed of a three-dimensional network based on interconnected slabs of boron (B12)ico icosahedra and (B6)oct octahedra. A linear [CBC] chain and nitrogen tightly bridges icosahedra. Sc partially occupies voids in the sheets of boron octahedra. It crystallizes with the trigonal space group P3m1, with Z=2. Lattice parameters (nm) are as follows: for RE: Sc, a,b=0.5568(4), c=1.0756(2); Y, a,b=0.55919(6), c=1.0873(2); Ho, a,b=0.55883(7), c=1.0878(6); Er, a,b=0.55889(5), c=1.0880(6); Tm, a,b=0.5580(1), c=1.0850(6); Lu, a,b=0.55771(9), c=1.0839(4). Magnetic characterization of ErB17C1.3N0.6 has been performed. 相似文献
164.
Mirka Bergamo Tiziana Beringhelli Giuseppe D'Alfonso Luca Garavaglia Pierluigi Mercandelli Massimo Moret Angelo Sironi 《Journal of Cluster Science》2001,12(1):223-242
Three and tetranuclear ring clusters have been obtained by treatment of [Re2(CO)8(THF)2] with carbonyl-rhenates containing two terminal hydrides. The reaction with [ReH2(CO)4]- provided a selective route to the previously known [Re3(-H)2(CO)12]- triangular cluster anion 1. The reaction with [Re2H2(-H)(CO)8]- gave the novel [Re4(-H)3(CO)16]- anion 2, containing a rare example of a puckered-square metal cluster. Protonation of 1 is known to afford the neutral [Re3(-H)3(CO)12] species 3. Analogously the reaction of 2 with a strong acid afforded the previously known square metal clusters [Re4(-H)4(CO)16] 4. The reaction could not be reversed by treatment with bases. Photolysis of 4 gave the unsaturated complex [Re2(-H)2(CO)8] 5: this is the reverse of the dimerization reaction, that in THF at room temperature produces 4 from 5. Thermal treatment (reflux in cyclohexane for 24 h) left 4 almost unchanged. A single crystal X-ray analysis of [NEt4]2 showed a s/e/s/s (e=eclipsed, s=staggered) conformation of the Re(CO)4 units, leading to a puckered geometry of the ring, at variance with the square-planar geometry of 4 (all eclipsed). Two of the three hydrides of 2 have been located as bridging the Re–Re edges from inside the metal ring, as previously observed in 4. Density functional computations indicated a puckered conformation as the most stable for both 2 and 4, with very low activation energies for ring inversion (6.6 and 2.2 kcal·mol-1, respectively), but ruled out solid state fluxionality for 4, whose observed planar geometry must be attributed to packing stabilization. 相似文献
165.
Summary A comparison of three binary mobile phases in LC separation of C60 and C70 fullerences on chemically bonded 2,4-dinitroanilinopropyl (DNAP) stationary phase was carried out, n-Hexane-benzene has been found to be the best mobile phase for efficient separation of the all-carbon molecules permitting high loads in preparative LC. 相似文献
166.
Zhen‐Yu Li Ping Chen Hong‐Gui Xu Shu‐Ying Peng Yi‐Ming Yang Zhong‐Zhen Zhao Yue‐Wei Guo 《Helvetica chimica acta》2007,90(7):1353-1359
Five new polycyclic Daphniphyllum alkaloids, macropodumines F ( 1 ) and G ( 2 ), 17‐oxoyuzurimine ( 3 ), and macropodumines H ( 4 ) and I ( 5 ), were isolated from the leaves of D. macropodum Miq ., collected in Sichuan Province, China. The structures and relative configurations of the new compounds – as well as of four known, related alkaloids – were elucidated on the basis of in‐depth spectroscopic and mass‐spectrometric analyses, by chemical derivatization, and by comparison of spectroscopic data with those of known compounds. 相似文献
167.
单分散二氧化钛超微粒子的制备 总被引:10,自引:0,他引:10
以四丁氧基钛为原料,采用溶胶-凝胶法制备了超微二氧化钛粉末.改变热处理气氛、升温速率、水与四丁氧基钛的摩尔比以及溶剂,分别得到7nm球形单相锐钛矿以及四方形(40nm×10nm)、球形(44nm)的主相金红石超微粒子. 相似文献
168.
The concept of crystalline module, that is, an unambiguously isolated, repeated quasi-molecular element, is introduced. This concept is more general than the concept of crystal lattice. The generalized modular approach allows extension of the methods and principles of crystallography to quasi-crystals, clusters, amorphous solids, and periodic biological structures. Principles of construction of aperiodic, nonequilibrium regular modular structures are formulated. Limitations on the size of icosahedral clusters are due to the presence of spherical shells with non-Euclidean tetrahedral tiling in their structure. A parametric relationship between the structures of icosahedral fullerenes and metal clusters of the Chini series was found. 相似文献
169.
Photocatalytic reactions occurring at semiconductor particles/solution interfaces can be applied to organic syntheses. In this review article, examples of photocatalytic syntheses of cyclic amino acids by suspended semiconductor particles, e.g., titanium(IV) oxide or cadmium(II) sulfide are introduced and interpreted. Different from the photocatalytic decomposition of pollutants under aerobic conditions, selective conversion of organic compounds can be driven by the photocatalytic reactions under deaerated conditions. 相似文献
170.
Zinc(II) Hydration in Aqueous Solution: A Raman Spectroscopic Investigation and An ab initio Molecular Orbital Study of Zinc(II) Water Clusters 总被引:1,自引:0,他引:1
Raman spectra of aqueous Zn(II)–perchlorate solutions were measured over broad concentration (0.50–3.54 mol-L–1) and temperature (25–120°C) ranges. The weak polarized band at 390 cm–1 and two depolarized modes at 270 and 214 cm–1 have been assigned to 1(a
1g), 2(e
g), and 5(f
2g) of the zinc–hexaaqua ion. The infrared-active mode at 365 cm–1 has been assigned to 3(f
1u). The vibrational analysis of the species [Zn(OH2)
2
+
] was done on the basis of O
h symmetry (OH2 as point mass). The polarized mode 1(a
1g)-ZnO6 has been followed over the full temperature range and band parameters (band maximum, full width at half height, and intensity) have been examined. The position of the 1(a
1g)-ZnO6 mode shifts only about 4 cm–1 to lower frequencies and broadens by about 32 cm–1 for a 95°C temperature increase. The Raman spectroscopic data suggest that the hexaaqua–Zn(II) ion is thermodynamically stable in perchlorate solution over the temperature and concentration range measured. These findings are in contrast to ZnSO4 solutions, recently measured by one of us, where sulfate replaces a water molecule of the first hydration sphere. Ab initio geometry optimizations and frequency calculations of [Zn(OH2)
2
+
] were carried out at the Hartree–Fock and second-order Møller–Plesset levels of theory, using various basis sets up to 6-31 + G*. The global minimum structure of the hexaaqua–Zn(II) species corresponds with symmetry T
h. The unscaled vibrational frequencies of the [Zn(OH2)
2
+
] are reported. The unscaled vibrational frequencies of the ZnO6, unit are lower than the experimental frequencies (ca. 15%), but scaling the frequencies reproduces the measured frequencies. The theoretical binding enthalpy for [Zn(OH2)
2
+
] was calculated and accounts for ca. 66% of the experimental single-ion hydration enthalpy for Zn(II).Ab initio geometry optimizations and frequency calculations are also reported for a [Zn(OH2)
2
18
] (Zn[6 + 12]) cluster with 6 water molecules in the first sphere and 12 in the second sphere. The global minimum corresponds with T symmetry. Calculated frequencies of the zinc [6 + 12] cluster correspond well with the observed frequencies in solution. The 1-ZnO6 (unscaled) mode occurs at 388 cm–1 almost in perfect correspondence to the experimental value. The theoretical binding enthalpy for [Zn(OH2)
2
18
] was calculated and is very close to the experimental single ion-hydration enthalpy for Zn(II). The water molecules of the first sphere form strong hydrogen bonds with water molecules in the second hydration shell because of the strong polarizing effect of the Zn(II) ion. The importance of the second hydration sphere is discussed. 相似文献