A nickel molybdenum phosphate with tunnel: Hydrothermal synthesis and structure of (NH3CH2CH2NH3)(4)center dot(NH3CH2CH2NH2)center dot Na center dot[Ni2Mo12O30(PO4)(HPO4)(4)(H2PO4)(3)]center dot 6H(2)O

A nickel molybdenum phosphate, (NH3CH2CH2NH3)(4).(NH3CH2CH2NH2). Na .[Ni2Mo12O30(PO4)(HPO4)(4)(H2PO4)(3)]. 6H(2)O, invoicing molybdenum present in V oxidation, has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. Deep brown-red crystals are formed in the triclinic system, space group P (1) over bar, a = 12,011(2), b = 14,612(3), c = 21.252(4) Angstrom, alpha = 80.54(2)degrees, beta = 83.10(2)degrees, gamma = 76.29(2)degrees, V = 3561.4(12) Angstrom(3), Z = 2, lambda(MoK alpha) = 0.71073 Angstrom (R(F) = 0.0529 for 9880 reflections), Data mere collected on a Siemens P4 diffractometer at 20 degrees C in the range of 1.75 degrees < theta < 23.02 degrees using the omega-scan technique. The structure was solved by direct methods using the program SHELXTL-93 and refined with the method of fun-matrix least-squares on F-2. The structure of the title compound may be considered to be two [Mo6O15(HPO4)(H2PO4)(3)](5-) units bonded together with a nickel atom, although several P-O groups are not protonated on account of coordination with a Na+ cation, The one-dimensional tunnels were formed in the solid of the title compound. A probe reaction of the oxidation of acetaldehyde with H2O2 using the title compound as catalyst was carried out in a liquid- solid system, showing that the title compound had high catalytic activity in the reaction, (C) 1999 Academic Press.

LaC_4~n(n=-2,-1,0,+1,+2)分子簇的结构与稳定性

本文用密度泛函方法研究了LaC4n(n=-2,-1,0,+1,+2)分子簇的结构与稳定性。振动频率分析表明，在所提出的九个构型中，当ｎ＝-2，0，+1，+2时，稀土位于碳环上最稳定，而当ｎ＝-1时，尽管稀土位于碳环上能量最低，但没有找到稳定的构型，我们的结果还指出，稀土元素是分子簇中对外部环境最敏感的部位，即最具有反应活性

A new dinuclear molybdenum(V)-sulfur complex containing citrate ligand: synthesis and characterization of K2.5Na2NH4[Mo2O2S2(cit)(2)].5H(2)O

The complex, K2.5Na2NH4[Mo2O2S2(cit)(2)]. 5H(2)O (1), was obtained by crystallization from a solution of (NH4)(2)MoS4, potassium citrate (K(3)cit) and hydroxyl sodium in methanol and water under an atmosphere of pure nitrogen at ambient temperature. The crystals are triclinic, space group , a = 7.376 (3)Angstrom, b = 14.620 (2) Angstrom, c = 14.661 (1) Angstrom, alpha = 71.10 (1)degrees, beta = 81.77 (1)degrees, gamma = 78.27(2)degrees, R = 0.0584 for 2545 observed (I > 2 sigma (I)) reflections. Single crystal structure analysis reveals that citrate ligand coordinated to molybdenum atom through two carboxylato oxygens and one deprotonated hydroxyl oxygen together with two bridging sulfur atoms and a terminal oxygen atom completes distorted coordination octahedron around each molybdenum atom. Principal dimensions are: Mo = O-t, 1.707 Angstrom (av); Mo-S-b, 2.341 Angstrom (av); Mo-O-(hydroxyl), 2.021 Angstrom (av); Mo-O(alpha-carboxyl), 2.1290 Angstrom (av) and Mo-O(beta-carboxyl), 2.268(av) Angstrom. IR spectrum is in agreement with the structure.

The use of half-sandwich iridium dithiolate and diselenolate complexes, Cp*Ir(L)(ER)(2) (L = CO, PMe3, PPh3; ER = SPh, SePh, SeMe), for the synthesis of heterodimetallic compounds. The molecular structure of Cp*Ir(CO)(mu-SePh)(2)[Mo(CO)(4)]

Carbonyl-iridium half-sandwich compounds, Cp*Ir(CO)(EPh)(2) (E = S, Se), were prepared by the photo-induced reaction of Cp*Ir(CO)(2) with the diphenyl dichalcogenides, E2Ph2, and used as neutral chelating ligands in carbonylmetal complexes such as Cp*Ir(CO)(mu-EPh)(2)[Cr(CO)(4)], Cp*Ir(CO)(mu-EPh)(2)[Mo(CO)(4)] and Cp*Ir(CO)(mu-EPh)(2)[Fe(CO)(3)], respectively. A trimethylphosphane - iridium analogue, Cp*Ir(PMe3)(mu-SeMe)(2)[Cr(CO)(4)], was also obtained. The new heterodimetallic complexes were characterized by IR and NMR spectroscopy, and the molecular geometry of Cp*Ir(CO)(mu-SePh)(2)[Mo(CO)(4)] has been determined by a single crystal X-ray structure analysis. According to the long Ir...Mo distance (395.3(1) Angstrom), direct metal-metal interactions appear to be absent. (C) 1998 Elsevier Science S.A. All rights reserved.

Synthesis and characterization of diblock copolymer of butadiene and 2-ethyl-2-oxazoline

By mechanism-transformation (anionic --> cationic) polymerization, diblock copolymer of butadiene and 2-ethyl-2-oxazoline (PBd-b-PEOx) was synthesized in two steps. The first step is the polymerization of butadiene block capped with ethylene oxide and its tosylation; the second step is the cationic ring-opening polymerization of 2-ethyl-2-oxazoline. The products were characterized by various methods, such as IR, (HNMR)-H-1, DMA, TEM and SAXS. The results show that the obtained copolymers possess high molecular weight and narrow molecular weighs distribution, and that the content of 1,4-structure was controllable.

Luminescence properties of rare earth (Eu3+ and Tb3+) complexes with conjugated carboxylic acids and 1,10-phenanthroline incorporated in silica matrix

Binary and ternary complexes of europium and terbium with conjugated carboxylic acid (nicotinic acid and 3,4-furandicarboxylic acid) and 1,10-phenanthroline were introduced into silica gel by the sol-gel method. The luminescence behavior of the complexes in silica gels was studied compared with the corresponding solid state complexes by means of emission, excitation spectra and lifetimes. The result indicated that the rare earth ions (EU3+ and Tb3+) showed fewer emission lines and slightly lower emission intensities in the silica gel than those in pure rare earth complexes. The lifetimes of rare earth ions (EU3+ and Tb3+) in silica gel doped with rare earth complexes became longer than those in pure rare earth complexes. (C) 1998 Elsevier Science S.A.

Structure, luminescence and magnetic properties of AgLnW(2)O(8) (Ln = Eu, Gd, Tb and Dy) compounds

Four new compounds AgLnW(2)O(8) (Ln = Eu, Gd, Tb and Dy) are prepared by solid-state reactions. They crystallize with a scheelite-related monoclinic symmetry. Infrared (IR) spectra show complicated absorption transitions in the region of 1000-400 cm(-1) that are similar to those of AgLnMo(2)O(8). Broad excitation and emission bands of the tungstate group are observed in AgGdW2O8 and AgTbW2O8 with a large Stokes shift, 12 573 and 12 387 cm(-1), respectively. Excitation and emission spectra of AgLnW(2)O(8) (Ln = Eu, Gd and Tb) show that energy transfer from the tungstate to EU3+, Gd3+ and Tb3+ occurs and that Eu3+ ions occupy a single crystallographic site with the C-2 Site symmetry. (C) 1997 Elsevier Science Ltd. All rights reserved.

The effect of structural parameters on the enthalpy relaxation of an inorganic glass (Li2O center dot 2SiO(2))

The structural relaxation process of an inorganic glass (Li2O . 2SiO(2)) at an ageing temperature of 703 K for an ageing time of 1 h has been studied by differential scanning calorimetry. A four-parameter model-the Tool-Narayanaswamy-Moynihan (TNM)-model was applied to simulate the normalized specific heat curve measured. A set of optimized parameters, Delta h*/R,beta,InA, and x was obtained. Then the effects of variation of each adjustable parameter on the calculated specific heat were summarized. (C) 1997 Elsevier Science S.A.

核磁共振方法表征2,2'-二(对羧酸苯氧基)-1,1'联萘

利用１Ｈ ＮＭＲ，１３Ｃ ＮＭＲ研究了 ２，２’－二（对羧酸苯氧基）－１，１’－联萘结构，并通过１Ｈ－１Ｈ ＣＯＳＹ及１３Ｃ－１Ｈ异核相关谱进一步确定了其１Ｈ谱和１３Ｃ谱中各谱峰的归属，为同类化合物的表征提供了一个依据。

1,4-二丙氧基-2,3-二氰基萘的合成

以1，4－萘醌为原料，经溴化、氰化、烷基化合成了1，4－二丙氧基－2，3－二氰基萘，用SiemensP4四圆衍射仪测得了晶体结构。合成方法简便，反应时间短，产率高。

1,4-二丙氧基-2,3二氰基萘的晶体结构

用 Siemens P4四圆衍射仪,测得了1,4-二丙氧基-2,3-二氰基萘的晶体结构。晶体属单斜晶系,空间群为 C2/C。晶格参数 a=14.987(3)A,b=10.527(2),c=11.755(2),β=118.98°(3),晶胞体积 V=1622.4(6)3,Z=4,Dc=1.205Kg/m~3,μ(MoK_α)=0.079mm~(-1),F(000)=624,T=293(2)K_o晶体结构应用直接法,解出最后的偏离因子 R=0.0554[1425个Ⅰ≥2σ(Ⅰ)衍射点]。结构分析表明,萘环的1,4和2,3位碳原子上的氢原子分别被丙氧基和氰基所取代,由于取代基的引入使萘环的结构有所改变。

Syntheses and crystal structures of [(C6H5CH2C5H4)(2)GdCl center dot THF](2) and (C6H5CH2C5H4)(2)ErCl center dot THF

[(C6H5CH2C5H4)(2)GdCl . THF](2) (1) and (C6H5CH2C5H4)(2)ErCl . THF (2) were prepared by the reaction of LnCl(3) (Ln=Gd, Er) with benzylcyclopentadienyl sodium in THF and characterized by elemental analysis, IR, H-1 NMR, C-13 NMR, MS and thermal gravimetry. The crystal structures of both compounds were determined. Complex 1 is dimeric and its structure belongs to the monoclinic, P2(1)/c space group with a=1.1432(2), b=1.2978(2), c=1.7604(3) nm, beta=108.75(2), V=2.4732(9) nm(3), Z=2(four monomers), D-c=1.54 g . cm(-3). R=0.0342 and R(w)=0.0362. Complex 2 is monomer and its structure belongs to the orthorhombic, P2(1)2(1)2(1) space group with a=0.8645(2), b=1.1394(3), c=2.5289(4) nm, V=2.4919(9) nm(3), Z=4, D-c=1.56 g . cm(-3). R=0.0514, R(w)=0.0529. The determination of the crystal structure shows that in complex 1 the benzyl groups on the cyclopentadienyls coordinated to Gd3+ are located in the opposite direction (139 degrees); in complex 2 the benzyl groups on the cyclopentadienyls coordinated to Er3+ are located in the same direction (6.5 degrees).

Synthesis and molecular structures of di- and trinuclear molybdenum complexes containing pyridine-2-thiolato (pyS) ligand

Dinuclear complexes [Mo-2(mu-pyS)(2)(CO)(4)(PPh(3))(2)] (1), [Mo-2(mu-pyS)(2)(CO)(5)(PPh(3))] (2) and a trace quality of trinuclear complex [Mo-3(mu-pyS)(2)(mu(3)-pyS)(2)(CO)(6)] (3) were obtained from the reaction of [Mo(CO)(3)(MeCN)(3)] with pyridine-2-thione (pySH) and PPh(3) in THF. The crystal structures of 1.2C(7)H(8) and 3.7 C7H8 have been determined by X-ray diffraction studies. Crystals of 1.2C(7)H(8) are monoclinic, space group C2/c and Z = 4, with a = 18.797(3), b = 11.143(4), c = 28.157(7) Angstrom, beta = 101.23(2)degrees. The structure was refined to R = 0.050 and Rw = 0.057 for 3146 observed reflections, Crystals of 3.7 C7H8 are monoclinic, space group P2(1)/a and Z = 4, with a = 13.912(2), b = 17.161(2), c = 15.577(3) Angstrom, beta = 101.17(1)degrees. The structure was refined to R = 0.046 and Rw = 0.051 for 4357 observed reflections. The molecule of 1 consists of two Mo(CO)(2)(PPh(3)) fragments linked by an Mo-Mo bond (2.974(2)Angstrom) and by two doubly-bridging pyS ligands. The compound 3 contains a bent open geometry of three molybdenum atoms (Mo(1)-Mo(2)-Mo(3) angle 122.99(3)degrees) linked by two Mo-Mo bonds (2.943(1) and 2.950(1) Angstrom) and by two doubly- and two triply-bridging pyS ligands.

[Z]-1-[2-(三芳基锡基)乙烯基]环辛醇的合成和性质

本文用三苯基氢化锡、三对甲苯基氢化锡作为锡氢化试剂与1-乙炔基环辛醇进行反应,合成了两个有机锡化合物:[Z]-1-[2-(三苯基锡基)乙烯基]环辛醇(1)和[Z]-1-[2-(三对甲苯基锡基)乙烯基]环辛醇(2),并测定了1的晶体结构.1和2分别与ICl,Br_2,I_2反应,得到六个有机锡一卤化物和三个有机锡二卤化物(3～11).有机锡二卤化物6和一卤化物5与KOH乙醇溶液反应,分别得到相应的锡氧化物和锡氢氧化物(12,13).有机锡二卤化物8分别与含氮双齿配体[2,2-联吡啶(Bipy),5-硝基-1,10-邻菲罗啉(Nphen),8-羟基喹啉(Oxin)]反应,得到三个相应的配合物(14～16).十六个新化合物通过元素分析、锡含量测定、IR、~1HNMR测定对其结构进行了表征,同时提出了1和2的生成反应历程.

LANTHANIDE PERCHLORATE COMPLEXES OF 1,4-BIS(PHENYLSULFINYL)BUTANE

Seven trivalent lanthanide perchlorate complexes of the types [Ln(bphab)(4)ClO4] (ClO4)2 (where La = La(III), Pr(III), Nd(III) and Eu(III)) and [Ln(bphab)(3)ClO4] (ClO4)(2) (where Ln = Ho(III), Er(III) and Lu(III), and bphab = 1,4-bis(phenylsulfinyl)butane) have been synthesized by the reaction of bphsb with lanthanide(III) perchlorate in methanol-chloroform mixture. The complexes have been characterized by elemental analyses, molar conductance, electronic and infrared spectral techniques. Several bonding parameters have been calculated from the absorption spectra of the Pr(III), Nd(III), Ho(III) and Er(III) complexes. Infrared spectral data suggest that bphsb acts as bidentate ligand coordinating through the oxygen atoms of the S=O moieties.