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991.
Zhou YL Zeng MH Liu XC Liang H Kurmoo M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(50):14084-14093
We present the synthesis, characterization of the structures, and magnetic properties of five isostructural dodecanuclear coordination clusters of Ni(II) and Co(II): [Co(12)(bm)(12)(NO(3))(O(2)CMe)(6)(EtOH)(6)](NO(3))(5) (1), [Ni(12)(bm)(12)(NO(3))(O(2)CMe)(6)(H(2)O)(3)(EtOH)(3)](NO(3))(5)·2H(2)O (2), mixed-metal composition (Ni/Co 1:1) [Co(6)Ni(6)(bm)(12)(NO(3))(O(2)CMe)(6)(NO(3))(5) (3), and [M(12)(bm)(12)(NO(3))(O(2)CMe)(6)(EtOH)(6)](ClO(4))(5) (M=Co (4), Ni (5)), in which Hbm=(1H-benzimidazol-2-yl)methanol. They consist of analogous structural cores that are constructed by three cubanes (M(4)O(4)) that surround the templating nitrate and bridging auxiliary acetate and the directing ligands bm. They have different magnetic behaviors. Whereas there is the absence of the out-of-phase ac susceptibility (χ') for the Ni(II)-based compounds 2 and 5, the Co(II)-containing compounds 1, 3, and 4 have prominent χ' signals that exhibit frequency dependence, which indicates slow magnetic relaxation behavior above 1.8 K. In particular, the larger perchlorate counterions in 4 further change the overall correlation interaction between clusters, thus leading to an enhanced blocking temperature for the less-symmetrical 4 (pseudo-C(3)) relative to 1 and 3 (true C(3)). Interestingly, electrospray ionization mass spectrometry (ESI-MS) indicates that the three dodecanuclear clusters of 1-3 retain their compositions in solution. The mixed-metal cluster cores of 3 are formed based on the nature of the interchangeability between metal centers in solution. 相似文献
992.
Jiménez MV Lahoz FJ Lukešová L Miranda JR Modrego FJ Nguyen DH Oro LA Pérez-Torrente JJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(29):8115-8128
The treatment of [{Rh(μ-SH){P(OPh)(3)}(2)}(2)] with [{M(μ-Cl)(diolef)}(2)] (diolef=diolefin) in the presence of NEt(3) affords the hydrido-sulfido clusters [Rh(3)(μ-H)(μ(3)-S)(2)(diolef){P(OPh)(3)}(4)] (diolef=1,5-cyclooctadiene (cod) for 1, 2,5-norbornadiene (nbd) for 2, and tetrafluorobenzo[5,6]bicyclo[2.2.2]octa-2,5,7-triene (tfb) for 3) and [Rh(2)Ir(μ-H)(μ(3)-S)(2)(cod){P(OPh)(3)}(4)] (4). Cluster 1 can be also obtained by treating [{Rh(μ-SH){P(OPh)(3)}(2)}(2)] with [{Rh(μ-OMe)(cod)}(2)], although the main product of the reaction with [{Ir(μ-OMe)(cod)}(2)] was [RhIr(2)(μ-H)(μ(3)-S)(2)(cod)(2){P(OPh)(3)}(2)] (5). The molecular structures of clusters 1 and 4 have been determined by X-ray diffraction methods. The deprotonation of a hydrosulfido ligand in [{Rh(μ-SH)(CO)(PPh(3))}(2)] by [M(acac)(diolef)] (acac=acetylacetonate) results in the formation of hydrido-sulfido clusters [Rh(3)(μ-H)(μ(3)-S)(2)(CO)(2) (diolef)(PPh(3))(2)] (diolef=cod for 6, nbd for 7) and [Rh(2)Ir(μ-H)(μ(3)-S)(2)(CO)(2)(cod)(PPh(3))(2)] (8). Clusters 1-3 and 5 exist in solution as two interconverting isomers with the bridging hydride ligand at different edges. Cluster 8 exists as three isomers that arise from the disposition of the PPh(3) ligands in the cluster (cis and trans) and the location of the hydride ligand. The dynamic behaviour of clusters with bulky triphenylphosphite ligands, which involves hydrogen migration from rhodium to sulfur with a switch from hydride to proton character, is significant to understand hydrogen diffusion on the surface of metal sulfide hydrotreating catalysts. 相似文献
993.
994.
Torrent-Sucarrat M Ruiz-Lopez MF Martins-Costa M Francisco JS Anglada JM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(18):5076-5085
We have investigated the HO(2) adsorption and acid dissociation process on the surface of (H(2)O)(20) and (H(2)O)(21) clusters by using quantum-chemistry calculations. Our results show that the radical forms a stable hydrogen-bond complex on the cluster. The HO(2) acid dissociation is more favorable in the case of the (H(2)O)(21) cluster, for which the inner water molecule plays a crucial role. In fact, acid dissociation of HO(2) is found to occur in two steps. The first step involves H(2) O autoionization in the cluster, and the second one involves the proton transfer from the HO(2) radical to the hydroxide anion. The presence of the HO(2) radicals on the surface of the cluster facilitates water autoionization in the cluster. 相似文献
995.
Todea AM Szakács J Konar S Bögge H Crans DC Glaser T Rousselière H Thouvenot R Gouzerh P Müller A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(24):6635-6642
The present study refers to a variety of reduced metal-oxide core-shell hybrids, which are unique with regard to their electronic structure, their geometry, and their formation. They contain spherical {Mo72Fe30} Keplerate-type shells encapsulating Keggin-type polyoxomolybdates based on very weak interactions. Studies on the encapsulation of molybdosilicate as well as on the earlier reported molybdophosphate, coupled with the use of several physical methods for the characterization led to unprecedented results (see title). Upon standing in air at room temperature, acidified aqueous solutions obtained by dissolving sodium molybdate, iron(II) chloride, acetic acid, and molybdosilicic acid led to the precipitation of monoclinic greenish crystals (1). A rhombohedral variant (2) has also been observed. Upon drying at room temperature, compound 3 with a layer structure was obtained from 1 in a solid-state reaction based on cross-linking of the shells. The compounds 1, 2, and 3 have been characterized by a combination of methods including single-crystal X-ray crystallography, magnetic studies, as well as IR, M?ssbauer, (resonance) Raman, and electronic absorption spectroscopy. In connection with detailed studies of the guest-free two-electron-reduced {Mo72Fe30}-type Keplerate (4) and of the previously reported molybdophosphate-based hybrids (including 31P NMR spectroscopy results), it is unambiguously proved that 1, 2, and 3 contain non-reduced Keggin ion cores and reduced {Mo72Fe30}-type shells. The results are discussed in terms of redox considerations (the shell as well as the core can be reduced) including those related to the reduction of "molybdates" by FeII being of interdisciplinary including catalytic interest (the MoVI/MoV and FeIII/FeII couples have very close redox potentials!), while also referring to the special formation of the hybrids based on chemical Darwinism. 相似文献
996.
997.
998.
This paper reports an automated analytical method for rapid determination of plutonium isotopes (239Pu and 240Pu) in environmental solid extracts. Anion exchange chromatographic columns were incorporated in a sequential injection (SI) system to undertake the automated separation of plutonium from matrix and interfering elements. The analytical results most distinctly demonstrated that the crosslinkage of the anion exchanger is a key parameter controlling the separation efficiency. AG 1-×4 type resin was selected as the most suitable sorbent material for analyte separation. Investigation of column size effect upon the separation efficiency revealed that small-sized (2 mL) columns sufficed to handle up to 50 g of environmental soil samples. Under the optimum conditions, chemical yields of plutonium exceeded 90% and the decontamination factors for uranium, thorium and lead ranged from 103 to 104. The determination of plutonium isotopes in three standard/certified reference materials (IAEA-375 soil, IAEA-135 sediment and NIST-4359 seaweed) and two reference samples (Irish Sea sediment and Danish soil) revealed a good agreement with reference/certified values. The SI column-separation method is straightforward and less labor intensive as compared with batch-wise anion exchange chromatographic procedures. Besides, the automated method features low consumption of ion-exchanger and reagents for column washing and elution, with the consequent decrease in the generation of acidic waste, thus bearing green chemical credentials. 相似文献
999.
采用基于密度泛函理论(DFT)的Dmol3程序系统研究了O原子与O2在 Au19与Au20团簇上的吸附反应行为. 结果表明: O在Au19团簇顶端洞位上的吸附较Au20强; 在侧桥位吸附强度相近. O与O2在带负电Au团簇上吸附较强, 在正电团簇吸附较弱. 从O―O键长看, 当金团簇带负电时, O―O键长较长, 中性团簇次之, 正电团簇中O―O键长较短, 因而O2活化程度依次减弱. 电荷布居分析表明, Au团簇带负电时, O与O2得电子数较中性团簇多, 而团簇带正电时, 得电子数较少. 差分电荷密度(CDD)表明, O2与Au团簇作用时, 金团簇失电子, O2的π*轨道得电子, 使O―O键活化. O2在Au19-团簇上解离反应活化能为1.33 eV, 较中性团簇低0.53 eV; 而在Au19+上活化能为2.27 eV, 较中性团簇高0.41 eV, 这与O2在不同电性Au19团簇O―O键活化规律相一致. 相似文献
1000.