SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF THE DAWSON-TYPE TUNGSTOPHOSPHATE HETEROPOLY COMPLEXES SUBSTITUTED BY NIOBIUM

Eight new complexes alpha(2)-M(7-m)H(m)[P2W17NbO62]. H2O and alpha-1, 2, 3-M(g-m)H(m) [P2W15Nb3O62]. XH(2)O(M=K, TMA, TEA, TBA) were synthesized and characterized by IR and UV spectroscopy, polarography, XPS and XRD methods. P-31 and W-183 NMR studies show that the niobium atoms in the anions are on the polar sites. The crystal of alpha-1, 2, 3-K7H2 [P2W15Nb3O62]. 30H(2)O is hexagonal, its cell parameters: a=1.9836(4), b=1.9836(9), c=1.5498(6)nm, alpha=beta=90 degrees, gamma=120 degrees.

SYNTHESIS AND CHARACTERIZATION OF TRISUBSTITUTED HETEROPOLYTUNGSTOGERMANATES CONTAINING GROUP 3A ELEMENTS

Six new compounds, alpha,beta-KaHb[GeW(9)M(3)(H2O)(3)O-37]. xH(2)O(M = Al, Ga, In; a + b = 7) and alpha-K9H5[Ge2W18Ga6(H2O)(3)O-74]. 20H(2)O, were synthesized from the lacunary precursors a and beta-GeW9O3410- and characterized by elemental analysis, spectroscopy and electrochemistry. Tungsten-183 NMR spectra of the title complexes consist of two lines with intensity ratio 2:1 as expected for trisubstituted heteropoly anions. The intensity ratio of alpha-Ga compound is 1:2, which is different from others(a:1). With the help of FAB mass spectrum, we concluded that it is a dimer with D-3h structure in aqueous, and the others exist by monomers with C-3v structures.

TETRAKIS(MU-DL-ALANINE-O-O')OCTA-AGUADIERBIUM(III) HEXAPERCHLORATE

The structure of the title compound, [Er-2(C3H7NO2)(4)- (H2O)(8)](ClO4)(6), consists of dimeric [Er-2(DL-alanine)(4)-(H2O)(8)](6+) cations and perchlorate anions. The four alanine molecules act as bridging ligands linking two Er3+ ions through their carboxyl O atoms. Each Er3+ ion is also coordinated by four water molecules to complete eightfold coordination in a square antiprism fashion. The perchlorate anions and the methyl groups of the alanine ligands are disordered.

A BINUCLEAR NICKEL(II) COMPLEX CONTAINING AN OXAMIDO-BRIDGE - SYNTHESIS, PROPERTIES AND X-RAY CRYSTAL-STRUCTURE OF [NI(OXAE)NI(PHEN)(2)](CLO4)(2)CENTER-DOT-3H2O

The binuclear complex [Ni(oxae)Ni(phen)2](ClO4)(2) . H2O (oxae=N,N'bis(2-aminoethyl) oxamido dianion, phen = 1, 10-phenanthroline) was prepared from the planar monomeric complex Ni(oxae) and characterized through analytical and spectroscopic measurements. The structure of [Ni(oxae)Ni(phen)(2)] (ClO4)2 . 3H(2)O was investigated by single-crystal X-ray analysis. The complex has an extended oxamido-bridged structure and consists of two nickel(II) ions, one of them in a square planar environment and another in a distorted octahedral environment. The Ni-Ni distance is 5.267 Angstrom.

PHASE-TRANSFER CHEMISTRY OF HETEROPOLYANIONS .1. RESEARCH ON SOLVATION BEHAVIOR OF SUBSTITUTED KEGGIN AND DAWSON ANIONS IN THE NONPOLAR-SOLVENTS

The heteropolyanions of the Keggin structure ZW(11)O(39)M(H2O)(n-)(Z = Si, Ge, P; M = Ni2+, Cu2+, Cr3+, Co2+, n = 4 similar to 6) and Dawson structure P(2)W(17)O(61)M(H2O)(n-)(M = Ni2+, Cu2+, Cr3+, Co2+, n = 7, 8) have been transferred into the non-polar

TERBIUM P-NITROBENZOATE HYDRATE

There are no discrete molecules of the title compound, catena-poly[{triaquaterbium-tris-beta-(p-nitro-benzoato)-O,O':O;O:O,O';O:O'-aqua(p-nitroben-zoato-O,O')terbium}-bis-mu-(p-nitrobenzoato-O:O') hydrate], [Tb2(C7H4NO4)6(H2O)5], in the crystal structure.

YTTRIUM SALICYLATE TETRAHYDRATE

The structure of tetraaqua-1kappa2O,2kappa2O-tetrakis-(mu-salicylato)-1:2kappa2O,1kappaO';1:2kappa2O,2kappaO';1kappaO:2kappaO';-1kappaO:2kappaO'-bis(salicylato)-1kappaO,O';2kappaO,O'-diyttrium tetrahydrate, [Y2(C7H5O3)6(H2O)4].4H2O, is composed of dimeri

CRYSTAL-STRUCTURES OF LN(NO3)(3) (LN=EU,LU) COMPLEXES WITH A CROWN-ETHER (16-CROWN-5)

The crystal structures of Ln(NO3)(3)(Ln = Eu,Lu) complexes with 16-crown-5 are reported. In [Eu(NO3)(2)(CH3CN)(16-crown-5)][Eu(NO3)(4)(H2O)2].1/2(16-crown-5) one Eu-III ion is coordinated to two bidentate nitrate ions, one acetonitrile molecule and five o

HOST-GUEST INTERACTIONS OF THIAMINE WITH ANIONS - CRYSTAL-STRUCTURE OF THIAMINE IODIDE SESQUIHYDRATE

The crystal structure of thiamine iodide sesquihydrate has been determined by X-ray diffraction methods as a host-guest model for coenzyme-substrate interactions. The asymmetric unit contains two chemical units. Both the thiamine molecules A and B, which are crystallographically independent, assume the usual F conformation and have a disordered hydroxyethyl side chain. An iodide anion (or a water molecule) bridges the pyrimidine and thiazolium rings of molecule A (or B) by forming a hydrogen bond with the amino group and an electrostatic contact with the thiazolium ring to stabilize the molecular conformation. In the crystal the thiamine molecules self-associate to form a pipe-like polymeric structure, in which four thiamine hosts surround an iodide guest and hold it through C(2)-H...I hydrogen bonds and thiazolium...I electrostatic interactions. Crystal data: C12H17N4OS+.I- . 1.5 H2O, monoclinic, P2(1)/c, a = 12.585(2), b = 25.303(5), c = 12.030(2) angstrom, beta = 115.15(1)degrees, V = 3468(1) angtrom3, Z = 8, D(c) = 1.606 g cm-3, R = 0.045 for 3328 observed reflections.

SYNTHESES, CHARACTERIZATION AND CRYSTAL-STRUCTURES OF THE COMPLEXES OF RARE-EARTH WITH O-CHLOROBENZOIC ACID

REL3.H2O (RE=Y, La is similar to Lu; HL = o-chlorobenzoic acid) were synthesized. Their thermal decomposition and IR spectra were studied. The crystal structures of the complexes of neodymium, terbium and lutetium were determined by X-ray diffraction method. They crystallize in the monoclinic space group P2(1)/n and show infinite chain structures. The coordination numbers of rare earth ions are nine.

THE SYNTHESES CHARACTERIZATION AND CRYSTAL-STRUCTURE OF RARE-EARTH COMPLEXES WITH L-PROLIN

The complexes of Ln(L-Pro)s(H2O)2(ClO4)3(Ln = Pr, Nd and Er. L-Pro = L-Proline) were synthesized and characterized by elemental analysis, IR. spectra and thermal analysis. The singal crystal Pr2(L-Pro)6(H2O)4(ClO4)6 Was also obtained. The crystal belongs to monoclinic, P2(1), a = 0.9879 (3) nm, b = 2.1883 (4) nm, c = 1.3393 (2)nm, beta = 91.23(2)-degrees, V = 2.895(1) nm3, Z = 2. R = 0.035 for 5032 observed reflections. The coordination polyhedron of Pr(III) ion comprises six oxygen atoms from L-Pro molecules and two water molecules. Each L-Pro molecule coordinates to two Pr(III) ions through its carboxyl group which serves as a bridging bidentate ligand to form onedimensional chain structure.

COMPARISON OF THE SULFURIZATION OF COMOK/AL2O3 CATALYST WITH H2S AND CS2

Only H2S consumption and H2O formation was found in the sulfurization of CoMoK/Al2O3 water gas shift catalyst with H2S/H-2. but CO2 was formed first, then CH4, H2O and H2S appeared in the later part of TPS with CS2/H-2. Carbon deposition on the catalyst during the sulfurization with CS2/H-2 caused a lower activity than the catalyst sulfurized with H2S but could be removed in the run of WGS reaction.

STRUCTURE OF CIS-DIAQUABIS(1,10-PHENANTHROLINE)ZINC SULFATE HEXAHYDRATE

[Zn(C12H8N2)2(H2O)2]SO4.6H2O, M(r) = 665.98, triclinic, P1BAR, a = 10.070 (4), b = 12.280 (3), c = 13.358 (2) angstrom, alpha = 109.12 (2), beta = 92.58 (2), gamma = 110.85 (2)-degrees, V = 1433.9 (7) angstrom 3, Z = 2, D(x) = 1.54 g cm-3, lambda(Mo K-alpha) = 0.71069 angstrom, mu = 10.1 cm-1, F(000) = 692, T = 293 K, R = 0.044 for 3985 observed reflections. The Zn atom is coordinated in a distorted octahedral geometry by four N atoms from two 1,10-phenanthroline (phen) ligands and two water molecules. The intermolecular ring-stacking interactions between the phen ligands occur in two forms: infinite chains and discrete dimers. Hydrogen bonds further stabilize the structure.

Serpentinization of peridotites from the southern Mariana forearc

A detailed petrologic and mineralogic study was carried out on serpentinized peridotites dredged from the southern landward slopes of the Mariana Trench, in order to reveal the serpentinization process of these unusual rocks and to identify the sole presence of the mineral lizardite. The constituent minerals of these southern Mariana forearc peridotites are olivine, amphibole and spinel, as well as serpentine, chlorite and talc. Compared with serpentinite seamounts, the serpentinized peridotites from the southern Mariana forearc are characterized by the absence of magnetite and brucite, and the common presence of talc; besides, the serpentine mineral variety is simplex, only lizardite. Combining mineral chemistry and mineral phase relationships, we conclude that (1) the absence of magnetite in the serpentinized peridotites is due to incomplete serpentinization, other than magnetite, the iron end-member in olivine forms Fe-rich brucite and Fe-rich serpentine; (2) brucite is not stable with high silica activity, reacting with later SiO2-rich fluid and then forming lizardite, leading to a lack of brucite in these serpentinized peridotites; (3) the occurrence of talc is the result of later SiO2-rich fluid reactions with lizardite; and (4) the reason for the sole occurrence of lizardite is that the temperature condition of our study area was not high enough for the formation of antigorite (which is stable at > 500 degrees C). Despite the broad overlap of lizardite and chrysotile in growth temperature, differences in the modes of occurrence of lizardite and chrysotile, such as the scarcity of H2O, low porosity and permeability, as well as the actual situation of initial serpentinization in the study area, result in the absolute prevalence of lizardite over chrysotile in the area. (C) 2009 National Natural Science Foundation of China and Chinese Academy of Sciences. Published by Elsevier Limited and Science in China Press. All rights reserved.

微孔配位聚合物的合成与表征

微孔配位聚合物是近年来被广泛研究的领域之一，这类材料在储气材料等领域的应用前景逐步被开发出来。作为良好的储气材料，配位聚合物必须具有规则的孔道结构和良好的稳定性。本论文以合成多维孔道新化合物为目标，成功合成并解析出13个微孔配位聚合物。对化合物的元素分析、红外和TGA等进行了表征，同时对部分化合物的紫外和荧光性质进行了测定。 首先，对微孔配位聚合物的最新研究动态进行了简要介绍，并对一些代表性化合物的结构类型、性能以及应用等进行了归纳总结。然后介绍了合成配位聚合物晶体的实验原理，化合物的表征方法。 本论文在水热条件下，成功合成了13个新化合物分别为：(C19H15N4)2(NO3)2∙3H2O (3-3)，(C19H15N4)2[CdCl4] (3-4)，2Ag(tta)∙AgNO3 (3-5)，Cu8(tta)15(H2O)Cl (3-6)，[Zn(5-CH3-tta)2(isoH)2] (BDC) (3-7)，Pb[(PO3)2C(OH) CH3]•H2O (4-1)，Ni(C5H4NCOO)2∙4H2O (5-2)，Co(C5H4NCOO)2(H2O)2∙2H2O (5-3)，[CdCl2(C13H12N2O)2] (5-4)，{C6H4(COOH)S}2 (5-5)，(Deta)(ClO4)NO3 (5-6)，(NH4)2[-Mo8O26] (6-1) 和 (NH4)2[Mo4O13] (6-2)。其中化合物3-5，3-6和3-7是由四氮唑和金属构筑的纳米孔道三维化合物；化合物3-3，3-4，5-2，5-3，5-4，5-5和5-6均具有超分子网络结构；4-1是有机膦酸为配体的二维层状化合物，是首例(5,5)连接的(47•63) (48•62)拓扑网络。化合物6-1是一维无限链骨架的钼酸盐，6-2是二维层状的钼酸盐，显示了不寻常的(32•4)(32•53•8)(3•42•54•6•82)(34•43•54•64) 拓扑网络。最后对论文进行概括总结，并展望了下一阶段的工作安排。