New high-dimensional networks based on polyoxometalate and crown ether building blocks

Three novel supramolecular assemblies constructed from polyoxometalate and crown ether building blocks, [(DB18C6)Na(H2O)(1.5)](2)Mo6O19.CH3CN, 1, and [{Na(DB18C6)(H2O)(2)}(3)(H2O)(2)]XMo12O40.6DMF.CH3CN (X = P, 2, and As, 3; DB18C6 = dibenzo-18-crown-6; DMF = N,N-dimethylfomamide), have been synthesized and characterized by elemental analyses, IR, UV-vis, EPR, TG, and single crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal space group P4/mbm with a = 16.9701(6) Angstrom, c = 14.2676(4) Angstrom, and Z = 2. Compound 2 crystallizes in the hexagonal space group P6(3)/m with a = 15,7435(17) Angstrom, c = 30.042(7) Angstrom, gamma = 120degrees, and Z = 2. Compound 3 crystallizes in the hexagonal space group P6(3)/m with a = 15.6882(5) Angstrom, c = 29.9778(18) Angstrom, gamma = 120degrees, and Z = 2. Compound 1 exhibits an unusual three-dimensional network with one-dimensional sandglasslike channels based on the extensive weak forces between the oxygen atoms on the [Mo6O19](2-) polyoxoanions and the CH2 groups of crown ether molecules, Compounds 2 and 3 are isostructural, and both contain a novel semiopen cagelike trimeric cation [{Na(DB18C6)(H2O)(2)}(3)(H2O)(2)](3+). In their packing arrangement, an interesting 2-D "honeycomblike" "host" network is formed, in which the [XMo12O40](3-) (X = As and P) polyoxoanion "guests" resided.

Synthesis and crystal structure of bis(tetrahydrofurfurylindenyl) lanthanide chlorides

Lanthanocene chlorides (C4H7OCH2C9H6)(2)LnCl[Ln=Y(1); Ln=Gd(2)] were synthesized by the reaction of tetrahydrofurfurylindenyl lithium(in situ) with corresponding anhydrous lanthanide chorides in THF. The crystal structures of these two complexes were determined by X-ray diffraction and they were unsolvated monomeric complexes. They were stable in the air for several hours. Complexes 1 and 2 belong to the same crystal system (orthorhombic) and space group(P2(1)2(1)2(1)). The unit cell dimensions of complex 1 were a=1.042 52(9) nm, b=1.47455(12) nm, c=1.497 99(13) nm, Z=4, D-c=1.508 g/cm(3); The unit cell dimensions of complex 2 were a=1.037 01(10) nm, b=1.472 33(12) nm, c=1.513 54(14) nm, Z=4, D-c=1.699 g/cm(3). They have the same structure and different space configurations. The central metal atom is coordinated by two indenyl, two oxygen of the tetrahydrofurfuryl and one chlorine atom to form a distorted trigonal bipyramid.

Hydrothermal synthesis and structure of [Ni(en)(2)V6O14](n)

A new complex [Ni (en)(2)V6O14](n) was hydrothermally synthesized and characterized by 2-dimensional vanadium oxide framework pillared by Ni(en)(2)group. Single crystal X-ray analysis indicates that this compound crystallizes in monoclinic system, space group P2(1)/c with a=0. 892 17(18) nm, b = 1. 711 1(3) nm, c=0. 662 73(13) nm, beta=111. 58(3)degrees, V=0.940 8(3) nm(3), Z=2, D-c=2.501 g/cm(3), R=0. 042 3, omegaR=0. 060 9, S=1. 006.

THE CLEAVAGE REACTION OF THE MO-MO TRIPLE BOND - THE CRYSTAL-STRUCTURES OF MOLYBDENUM COMPLEXES [CPMO(CO)(2)(C(5)H(4)NS)], [CPMO(CO)(2)(C(9)H(6)NS)]O=PPH(3) AND [CPMO(CO)(2)(S(2)CNME(2)]

The reactions of [Cp2Mo2(CO)4] (1) with 2,2'-dipyridyl disulphide (C5H4NS-)2, 8,8'-diquinolyl disulphide (C9H6NS-)2 and tetramethyl thiuram disulphide (Me2NC(S)S-)2 in toluene solution resulted in the cleavage of the Mo-Mo triple bond to yield molybdenum complexes [CpMo(CO)2(C5H4NS)] (2), [CpMo(CO)2(C9H6NS)] (3) and [CpMo(CO)2(S2CNMe2)] (4), respectively. The molecular structures of 2, 3 . O=PPh3 and 4 were determined by X-ray diffraction studies. Crystals of 2 are monoclinic, space group P2(1)/n, with Z = 4, in a unit cell of dimensions a = 6.448(1), b = 12.616(2), c = 14.772(2) angstrom, beta = 92.85(1)-degrees. The structure was refined to R = 0.028 and R(w) = 0.039 for 1357 observed reflections. Crystals of 3 . O=PPh3 are triclinic, space group P1BAR, with Z = 2, in a unit cell of dimensions a = 11.351(3), b = 13.409(3), c = 9.895(2) angstrom, alpha = 94.59(2), beta = 90.35(2), gamma = 78.07(2)-degrees. The structure was refined to R = 0.033 and R(w) = 0.037 for 3260 observed reflections. Crystals of 4 are monoclinic, space group P2(1)/a and Z = 4 with a = 12.468(5), b = 7.637(2), c = 13.135(4) angstrom, beta = 96.62(3). The structure was refined to R = 0.032 and R(w) = 0.042 for 1698 observed reflections. Each of complexes 2-4 contains a cyclopentadienyl ligand, a cis pair of carbonyls and a chelate ligand (S,N donor or S,S donor). All the compounds have distorted square-pyramid structures.

[(t-BuCp)_2PrCl]_2的合成和晶体结构

叔丁基环戊二烯钠和无水三氯化镨在四氢味喃中反应,产物经过甲苯处理,分离得到配合物[(t-BuCp)_2PrCl]_2对该配合物进行了元素分析,红外光谱和~1HNMR表征。同时测得了它的单晶结构。该配体属正交晶系,C_(mca)空间群,晶胞参数为:a=2.378(6)nm,b=0.9565(1)nm,c=1.6455(4)nm,V=3.743nm~3,Z=4。R=0.042。Pr—Cl键长为0.2864nm。Pr-Cent(环中心)为0.2489nm。Pr-Pr(a)为0.4041nm。

钛在草酸溶液中腐蚀行为的XPS研究

本文首次用X-光电子能谱(XPS)技术研究了H_2C_2O_4溶液中钛基的腐蚀行为,对Ti基片的表面和界面进行了XPS表征.实验结果表明:Ti基在80℃,10%的草酸溶液中腐蚀两小时,样品的表面只有Ti~0和TiO存在;经过四小时腐蚀的样品表面主要是TiO_2和少部分Ti~(2+).这与X-衍射分析认为有TiH_(1.042)的结构看法相符。同时,Ti0_2与表面涂层RuO_2都属金红石型结构,因而完全有可能形成牢固的金属阳极材料。

大洋岛屿玄武岩低温蚀变作用及其对大洋过渡金属循环的贡献

用化学方法和ICP—MS方法分别对中、西太平洋海山富钴铁锰结壳产出区玄武岩的主元素、 微量元素和稀土元素(REE)含量进行了测定，结果表明，研究区玄武岩经受了强烈的洋底低温蚀 变作用，主元素成分发生了明显的变化，失去了原岩的特征．样品与新鲜大洋岛屿玄武岩(OIB) 极为相似的稀土元素配分模式和微量元素含量特征表明，所研究的岩石属典型的大洋板内玄武 岩．受洋底低温蚀变作用的影响，样品的Al O。，Fe O。，MnO、K O，P O 含量增加，MgO，FeO 的 含量降低．蚀变作用使大洋岛屿玄武岩中的镁、铁等活动组分大量流失，从而表现出相对富SiO 的特征(标准矿物计算结果中出现石英)． 由于蚀变作用，活动组分的流失使样品的REE相对富 集，而富REE铁锰氧化物在玄武岩气孔和裂隙中的沉淀不仅使样品的REE含量增大，而且引起 轻稀土元素(LREE)与重稀土元素(HREE)分馏，表现为Σf(Ce)／Σf(Yb)值增大． 以REE 富集 机制为基础，对样品中铁锰氧化物的沉淀量和单位质量新鲜玄武岩中活动组分的流失量进行了理 论计算，结果表明，因低温蚀变作用所引起的新鲜玄武岩的单位质量亏损为0．150t0．657，而单 位质量新鲜玄武岩中铁锰氧化物的沉淀量为0．006t0．042．主元素中以铁、镁的流失亏损最为明 显，新鲜玄武岩中铁、镁的流失比例分别为18．28 ～70．95 和44．50％～93．94％ ，超过了岩石 总量的流失亏损比例(15．0 ～65．7 )，因而样品相对贫铁、镁．其他元素的流失量和流失比例 都很好地印证了地球化学研究的结果．样品中铝、钾、磷负的流失量是由于沸石在岩石气孔中的充 填和岩石的磷酸盐化．理论计算结果和地球化学研究都表明，大洋岛屿玄武岩的低温蚀变向海水 提供了大量金属，这是大洋海水中金属循环的重要环节．