Small Heteroborane Cluster Systems. 6. Mössbauer Effect Study of Iron Substituted Small Metallaborane Clusters

The M?ssbauer effect spectra for a series of small [Fe(eta(5)-C(5)H(5))(CO)(x)()] substituted metallaborane complexes are reported, where x = 1 or 2. The pentaborane cage in compounds [Fe(eta(5)-C(5)H(5))(CO)(2)B(5)H(7)P(C(6)H(5))(2)] (1), [Fe(eta(5)-C(5)H(5))(CO)(2)B(5)H(8)] (2), and [(Fe(eta(5)-C(5)H(5))(CO)(2))(2)B(5)H(7)] (3) was found to act as a significantly better donor ligand than the ligands in a comparison group of previously reported [Fe(eta(5)-C(5)H(5))(CO)LX] complexes, where L = CO or PPh(3) and X = halide, pseudohalide, or alkyl ligands. These metallaborane complexes were found to most resemble their silyl analogues in M?ssbauer spectral parameters and the electronic distribution around the iron centers. In addition, the M?ssbauer data showed that the [&mgr;-2,3-(P(C(6)H(5))(2)B(5)H(7)](-) ligand was a superior donor to the corresponding unsubstituted [B(5)H(8)](-) ligand. The M?ssbauer spectral results for the metallaborane complexes studied were found to be in general agreement with the anticipated donor and accepting bonding considerations for the cage ligands based upon their infrared and (11)B NMR spectra and X-ray structural features. The M?ssbauer data for the [Fe(eta(5)-C(5)H(5))(CO)B(4)H(6)(P(C(6)H(5))(2))] (4) and [Fe(eta(5)-C(5)H(5))(CO)B(3)H(7)(P(C(6)H(5))(2))] (5) complexes, in comparison with compound 1, showed that as the borane cage becomes progressively smaller, it becomes a poorer donor ligand. A qualitative relationship was found between the observed M?ssbauer isomer shift data and the number of boron cage vertices for the structurally related [Fe(eta(5)-C(5)H(5))(CO)(x)B(y)H(z)P(C(6)H(5))(2)] complexes, where x = 1 or 2, y = 3-5, and z = 6 or 7. The X-ray crystallographic data for compounds 1, 2, 5, and [Fe(eta(5)-C(5)H(5))(CO)B(5)H(8)] (6) were also found to agree with the trends observed in the M?ssbauer spectra which showed that the s-electron density on the iron nucleus increases in the order 5 < 6 < 2 < 1. The X-ray crystal structure of complex 2 is also reported. Crystallographic data for 2: space group P2(1)/c (No. 14, monoclinic), a = 6.084(3) ?, b = 15.045(8) ?, c = 13.449(7) ?, beta = 99.69(5) degrees, V = 1213(1) ?(3), Z = 4 molecules/cell.     

Isotachophoretic zone formation of serum albumin in different free fluid electrophoresis instruments

The isotachophoretic behavior of a model protein, serum albumin, was examined (i) by computer simulation, (ii) by capillary isotachophoresis in HPE 100 and Tachophor 2127, (iii) by continuous flow isotachophoresis in Elphor VaP 22 and the BIO-STREAM Separator and (iv) by recycling isotachophoresis in an apparatus of our own design. Variations in monitored zone shapes can be explained by differences in engineering aspects and fluid stabilization principles of the instruments.     

Mo(W)-Cu(Ag)-S簇合物的非线性光学性能研究

本文介绍了非线性光学性测试中的Ｚ－扫描方法。总结了Ｍｏ（Ｗ）－Ｃｕ（Ａｇ）－Ｓ簇合物的光限制效应、非线性吸收和非线性折射等光学性质。讨论了簇合物结构与光学性能的关系。     

锆助剂对低温液相合成甲醇用铜铬硅催化剂性能的影响

考察了含锆的铜铬硅催化剂低温液相合成甲醇性能，并进行了BET、TPR-H2、TPD-H2、TPD-CO、XRD和XPS表征。结果表明，锆作为结构助剂及电子助剂对催化剂在低温液相合成甲醇反应中具有显著的促进作用，反应活性可提高32.25 ％。锆助剂能有效提高催化剂的比表面积，促进催化剂中铜铬组分的分散及表面富集。ZrO2加入在催化剂表面产生的Cu+与催化活性的改善密切相关，Zr4+、Cr3+、Cu+可形成复合中心，为价态的稳定性提供微环境，在H2活化及C O键的断裂等反应步骤中起重要作用。     

Synthesis and Catalytic Application of Homo-bimetallic Metallocene Complexes as Ethylene Polymerization Catalysts

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Polyoxometalate Derivatives with Multiple Organic Groups. 2. Synthesis and Structures of Tris(organotin) alpha, beta-Keggin Tungstosilicates

Eight tris(organotin)-substituted Keggin tungstosilicate heteropolyanions have been synthesized and characterized by elemental analysis, infrared and M?ssbauer spectroscopy, multinuclear NMR, and X-ray crystallography. The new anions contain alpha- or beta-SiW(9)O(34)(10)(-) moieties and are of two structural types, [(RSn)(3)(SiW(9)O(37))](7)(-) (R, isomer: Ph, alpha-, 1; n-Bu, alpha-, 2; Ph, beta-, 3; n-Bu, beta-, 4) and [(RSnOH)(3)(SiW(9)O(34))(2)](14)(-) (Ph, alpha-, 5; n-Bu, alpha-, 6; Ph, beta-, 7; n-Bu, beta-, 8). Crystals of Cs(4)H(3)[(PhSn)(3)(SiW(9)O(37))].8H(2)O (anion 3) are monoclinic, space group C2/c, with lattice constants a = 48.91(2) ?, b = 12.111(3) ?, c = 20.334(9) ?, beta = 102.30 degrees, and Z = 8. The anion has nominal C(3)(v)() symmetry and has a structure with three corner-shared WO(6) octahedra of the beta-Keggin anion replaced by three PhSnO(5) groups. Crystals of Cs(9)H(5)[(BuSnOH)(3)(SiW(9)O(34))(2)].36H(2)O (anion 6) are tetragonal, space group P&fourmacr;2(1)m, with lattice constants a = b = 29.005(4) ?, c = 13.412(4) ?, and Z = 4. The anion has the anticipated D(3)(h)() symmetry and contains three BuSnOH groups sandwiched between A,alpha-SiW(9)O(34)(10)(-) anions.     

Controlled synthesis and magnetic properties of 2D and 3D iron azide networks infinity2[Fe(N3)2(4,4'-bpy)] and infinity3[Fe(N3)2(4,4'-bpy)

Controlled synthesis of transition metal complexes with mixed ligands has led to two new compounds with the same empirical formula [Fe(N3)2(4,4'-bpy)] (4,4'-bpy=4,4'- bipyridine). The compound 2D-[Fe(N3)2(4,4'-bpy)] (I) contains end-on (EO) bridging azido ligands. It crystallizes in the orthorhombic crystal system, space group Cmmm (No. 65): a=11.444(2) A, b=15.181(3) A, c=3.458(1) A, V=600.8(2) A(3), and Z=2. The compound 3D-[Fe(N3)2(4,4'-bpy)] (II) contains end-to-end (EE) azido bridges. It belongs to the tetragonal crystal system, space group P4(1)2(1)2 (No. 92): a=8.132(1) A, b=8.132(1) A, c=16.708(3) A, V=1104.9(5) A(3), and Z=4. Crystals of I and II have been grown by the diffusion method. Phase-pure samples of both compounds have been obtained by means of an optimal solution synthesis. Spontaneous long-range magnetic ordering was found in both I and II, with I being a metamagnet, and II being a ferromagnet. For I, in the low-field region, multiple transitions at TN1=20 K and TN2=5 K were observed, and these indicated the existence of Fe moment reorientation. Heat capacity measurements on II confirmed ferromagnetic transition at TC=20 K.     

Nanocrystalline iron oxide aerogels as mesoporous magnetic architectures

We have developed crystalline nanoarchitectures of iron oxide that exhibit superparamagnetic behavior while still retaining the desirable bicontinuous pore-solid networks and monolithic nature of an aerogel. Iron oxide aerogels are initially produced in an X-ray-amorphous, high-surface-area form, by adapting recently established sol-gel methods using Fe(III) salts and epoxide-based proton scavengers. Controlled temperature/atmosphere treatments convert the as-prepared iron oxide aerogels into nanocrystalline forms with the inverse spinel structure. As a function of the bathing gas, treatment temperature, and treatment history, these nanocrystalline forms can be reversibly tuned to predominantly exhibit either Fe(3)O(4) (magnetite) or gamma-Fe(2)O(3) (maghemite) phases, as verified by electron microscopy, X-ray and electron diffraction, microprobe Raman spectroscopy, and magnetic analysis. Peak deconvolution of the Raman-active Fe-O bands yields valuable information on the local structure and vacancy content of the various aerogel forms, and facilitates the differentiation of Fe(3)O(4) and gamma-Fe(2)O(3) components, which are difficult to assign using only diffraction methods. These nanocrystalline, magnetic forms retain the inherent characteristics of aerogels, including high surface area (>140 m(2) g(-1)), through-connected porosity concentrated in the mesopore size range (2-50 nm), and nanoscale particle sizes (7-18 nm). On the basis of this synthetic and processing protocol, we produce multifunctional nanostructured materials with effective control of the pore-solid architecture, the nanocrystalline phase, and subsequent magnetic properties.     

Hydrogen storage in the dehydrated prussian blue analogues M3[Co(CN)6]2 (M = Mn, Fe, Co, Ni, Cu, Zn)

The porosity and hydrogen storage properties for the dehydrated Prussian blue analogues M3[Co(CN)6]2 (M = Mn, Fe, Co, Ni, Cu, Zn) are reported. Argon sorption isotherms measured at 87 K afford BET surface areas ranging from 560 m2/g for Ni3[Co(CN)6]2 to 870 m2/g for Mn3[Co(CN)6]2; the latter value is comparable to the highest surface area reported for any known zeolite. All six compounds show significant hydrogen sorption at 77 K and 890 Torr, varying from 1.4 wt % and 0.018 kg H2/L for Zn3[Co(CN)6]2 to 1.8 wt % and 0.025 kg H2/L for Cu3[Co(CN)6]2. Fits to the sorption data employing the Langmuir-Freundlich equation give maximum uptake quantities, resulting in a predicted storage capacity of 2.1 wt % and 0.029 kg H2/L for Cu3[Co(CN)6]2 at saturation. Enthalpies of adsorption for the frameworks were calculated from hydrogen isotherms measured at 77 and 87 K and found to increase with M varying in the order Mn < Zn < Fe < Co < Cu < Ni. In all cases, the binding enthalpies, which lie in the range of 5.3-7.4 kJ/mol, are higher than the 4.7-5.2 kJ/mol measured for Zn4O(1,4-benzenedicarboxylate)3.