基于2-氨基吡啶的两个簇基超分子化合物的合成、 结构及催化性能

以磷钼酸、 2-氨基吡啶、 五氧化二钒、 氯化锌和氯化镍等为主要原料, 采用水热方法合成了2个簇基超分子化合物[H₃PMo₁₂O₄₀]₂[C₅H₆N₂]₆(1)和[H₂PMo₁₂V₂O₄₂][C₅H₆N₂]₅·3H₂O(2)(C₅H₆N₂=2-氨基吡啶). 通过元素分析、 红外光谱、 紫外-可见光谱、 X射线光电子能谱、 热重分析、 X射线单晶衍射及X射线粉末衍射等手段对化合物进行了结构表征. 结构分析显示, 簇单元不同的2个超分子化合物以各自独特的堆积方式形成三维超分子网络. 利用苯乙烯的环氧化反应研究了2个化合物的催化性能.     

The reaction of cis dioxobis(2,4 pentanedionato)molybdenum (VI) and 2,2′ pyridylbenzoxazole (L), a novel route to β[Mo8O26]

MoO₂(C₅H₇O₂)₂, where C₅H₇O₂ is 2,4-pentanedione (acac), reacts with 2-2′ pyridylbenzoxazole in acetone to give a product with stoichiometry, Mo₃C₂₄H₁₆N₆O₁₂. This product dissolves readily in dimethylformamide to give a brown solution which on standing for several weeks yielded crystals. An X-ray structure determination showed these crystals to contain uncoordinated 2-2′pyridylbenzoxazole and [(CH₃)₂NH₂]₄⁺[Mo₈O₂₆]⁴⁻.     

Studies on Organo-Phosphorus, -Arsenic and -Antimony Polytungstates and Polymolybdates (Ⅶ)——Preparation and Properties of p-Aminophenylarsenic Polymolybdates

In order to investigate the influence of organic groups on the types of organoarsenic polymolybdates, the reations of p-aminophenylarsonic acid with sodium molybdate were tested at pH=3-5. Six salts were prepared and characterized. (1) (CN3H8)4 [(p-NH3C6H4As)2Mo6O25] · H2O, (2) (CN3H6)4 [(p-, NH3C6H4As )2Mo6O25 ] · 6H20, (3) Cs4 [(p-NH3C6H4As)2Mo6O25] · 4H2O, (4) C(CH3)4N]4[(p-NH3C6H4As)2Mo6O25] · 5H2O, (5) [(n-C4H9)4N]3Na[(p-NH3C6H4As)2Mo6O25] · 2H2O, (6) Ba2 NH3C6H4As)2Mo6O25] · 10H2O. The IR, UV spectra, and electrochemical behavior are reported and discussed. They should belong to the same type as that for phenyl derivative or the nitrophenyl derivatives. But the ammo groups can accept protons, so that the anion' s charge decreases. Very similar to the tungsten congener (CN3H6)4[(p-NH3C,H4As)2W6O25] · 4H2O, [(RAs)2Mo6O25]4- type of complexes are formed.     

Thermal decomposition study on mixed ligand thymine complexes of divalent nickel(II) with dianions of some dicarboxylic acids

Thermal decomposition of mixed ligand thymine (2,4-dihydroxy-5-methylpyrimidine) complexes of divalent Ni(II) with aspartate, glutamate and ADA (N-2-acetamido)iminodiacetate dianions was monitored by TG, DTG and DTA analysis in static atmosphere of air. The decomposition course and steps of complexes [Ni(C₅H₆N₂O₂)(C₄H₅NO₄)²⁻(H₂O)₂]·H₂O, [Ni(C₅H₆N₂O₂)(C₅H₇NO₄)²⁻(H₂O)₂]·H₂O and [Ni(C₅H₆N₂O₂)(C₆H₈N₂O₅)²⁻(H₂O)₂]·1.5H₂O were analyzed. The final decomposition products are found to be the corresponding metal oxides. The kinetic parameters namely, activation energy (E*), enthalpy (ΔH*), entropy (ΔS*) and free energy change of decomposition (ΔG*) are calculated from the TG curves using Coats–Redfern and Horowitz–Metzger equations. The stability order found for these complexes follows the trend aspartate > ADA > glutamate.     

Third-order Optical Nonlinearities of a Series of Compounds Derived from a Keplerate Type Molybdenum-oxide-based Polyoxometalate

Abstract By reacting the unique Keplerate type molybdenum-oxide based polyoxometalate （NH4）42·[MoI320372·（CH3COO）30（H2O）y2]·ca.300H2·ca. 10CH3COONH4（1） with tetramethylammonium bromide, a new derivative （NH4）26[TMA]16{MoI32O372（H2O）72（CH3COO）30}·ca.7NH4CH3COO·ca.189H2O（2, TMA=tetramethylammonium） was prepared. Compound 2 was characterized by Fourier transform infrared spectroscopy（FTIR）, UV-Vis, elemental and thermogravimetric analyses. By the well-established Z-scan technique, investigations on the nonlinear opti- cal（NLO） properties of the series of compounds derived from the Keplerate type molybdenum-oxide-based poly- oxometalate, namely, the newly prepared compound 2, the three previously reported compounds, included compound 1, （NH4hs（TBA）24{Mo132O372（H2O）72（CH3COO）30}·ca.7NH4CH3COO·ca. 173H2O（3, TBA=tetrabutylammonium） and （DODA）40（NH4）2[（H2O）nMo132O372（CH3COO）3o（H20）72]（4, DODA=dimethyldioctadecylammonium）, reveal that the third-order nonlinearity[x（3）] values of compounds 1, 2 and 3 in the DMF/H2O solution and compound 4 in chloro- form are almost the same, which indicates that the counter cations with different length of alkyl chains show ignora- ble impacts on the NLO susceptibility. In other words, the remarkable third-order nonlinearities[x（3）≈10 19 m2/V2] mainly come from the [MoI32O372（CH3COO）30（H2O）72]42 anions. This fact reveals that the applications of the NLO active polyoxometalates in various environments（such as hydrophilic, hydrophobic, polar, apolar, etc.） can be achieved by simply varying cations to meet the demands in the design of diverse devices. Keywords Keplerate type polyoxometalate; Nonlinear optical property; Z-Scan technique; Self-defocusing; Reverse saturable absorption     

Hydrothermal Synthesis,Structure and Properties of a New Phosphomolybdate Based on Novel [Co(H2O)4(HP2Mo5O23)]8- Anions and [H8(H2O)16]8+ Water Cluster Cations

A pure inorganic [P₂Mo₅O₂₃]^6- based cobalt complex [H₈(H₂O)₁₆][Co(H₂O)₄(HP₂Mo₅O₂₃)₂] with a sandglass-like shape was synthesized and characterized by means of single-crystal X-ray diffraction, powder X-ray diffraction(PXRD), infrared spectroscopy(IR), thermogravimetry/differential scanning calorimetry(TG/DSC), ultraviolet-visible spectroscopy(UV-Vis) and cyclic voltammogram(CV). Single-crystal X-ray diffraction analysis reveals that the asymmetric unit of compound 1 consists of a half cobalt ion, one [P₂Mo₅O₂₃]^6- anion, two coordinated water molecules and eight lattice water molecules. It is especially intriguing to note that two [P₂Mo₅O₂₃]^6- clusters are symmetrical about the Co ion, like a sandglass. And a chair-like water cluster with an unprecedented centrosymmetric [H₈(H₂O)₁₆]⁸⁺ can be observed in compound 1. Additionally, the electrochemical and catalytic properties of compound 1 were also investigated.     

trz-Cl-Cu-PMo12的合成、 表征及催化氧化碘离子性能

以H₃PMo₁₂O₄₀为前驱体, 采用水热法使1,2,4-三氮唑-3-甲酸进行原位脱羧后, 合成了1,2,4-三氮唑修饰的Keggin型多金属氧酸盐基金属-有机框架化合物(trz-Cl-Cu-PMo₁₂), 并通过X射线单晶衍射、 红外光谱(IR)、 热重分析(TG)、 X射线衍射(XRD)、 扫描电子显微镜(SEM)及元素分析等手段对其进行了表征. X射线单晶衍射及元素分析表明, 该晶体化合物的结构式为[Cu₆Cl_0.5(C₂H₂N₃)₄][PMo₁₂O₄₀][Cu₆Cl_0.5(C₂H₂N₃)₄], 且由1个经典的 Keggin 型[PMo₁₂O₄₀]^3-和2个[Cu₆Cl_0.5(C₂H₂N₃)₄]^1.5+以近似中心对称的方式构成, 各组分之间通过超分子作用形成一维(1D)~三维(3D)结构. 催化性能研究结果表明, 该非均相催化剂在催化过氧化氢氧化碘离子为碘单质的反应中, 经4 min 35 s到达终点时, 反应速率高达1.42×10^-5 mol·L^-1· s^-1, 碘单质生成速率提高了约551倍. 催化剂重复使用8次, 转化率仍然高达99.6%, 表现出优异的催化活性, 且具有良好的可重复性.     

Synthesis and X-ray structure of the Mo(VI) species Mo4O12(C12H30N4S2)2(C3H7ON)n (n ≈ 2)

Dissolution of Mo₂O₅((CH₃)₂NCH₂CH₂NHCH₂CH₂S)₂ in dimethylformamide results in the formation of a species without coordinated sulphur, as indicated by ⁹⁵Mo NMR spectroscopy. Subsequent crystallization of this solution yielded the compound Mo₄O₁₂(C₁₂H₃₀N₄S₂)₂(C₃H₇ON)₂ which X-ray crystallography shows to consist of a novel Mo₄O₁₂ core, containing an eight-membered Mo₄O₄ ring with the two pairs of diagonal molybdenum atoms linked by disulphido-containing groups.     

Template-directed Synthesis of Three Metal Oxalates via 4-Connected Building Units

Three novel compounds, [Co（en）3]2[Zr2（C2O4）7]·2H20（HNU-2, en=ethylenediamine）, [Co（NH3）6]· [Ce（CzO4）3（H2O）]·H2O（HNU-3） and [Co（dien）2][Gd（C2On）3]·0.75H2O（HNU-4, dien=dethylenetriamine） were hydro- thermal synthesized based on the templates of [Co（en）3]C13, [C0（NH3）6]C13 and [Co（dien）2]C13, respectively. The Zr4＋ Ce3＋ and Gd3＋ cations are all coordinated by four oxalates to form [M（C2O4）n（H2O）n]m （M=Zr, Ce or Gd; n=0 or 1; m=4 or 5）, which are similar to [In（C2O4）4]5- in NKB-1, and can be regarded as 4-connected building units. The [M（C2O4）a（H2O）n]m units are connected via sharing the bis-bidentate bridging oxalate ligands to form binuclears in HNU-2 and 1D ＂zigzag＂ chains in HNU-3 and HNU-4. cular building units to design 3D open frameworks with It is suggested that these compounds could be used as mole- zeolite topologies.     

Hydrothermal syntheses and crystal structures of bimetallic cluster complexes [{Cd(phen)2}2V4O12]·5H2O and [Ni(phen)3]2[V4O12]·17.5H2O

The hydrothermal reactions of vanadium oxide starting materials with divalent transition metal cations in the presence of nitrogen donor chelating ligands yield the bimetallic cluster complexes with the formulae [{Cd(phen₂)₂V₄O₁₂]·5H₂O (1) and [Ni(phen)₃]₂[V₄O₁₂]·17.5H₂O (2). Crystal data: C₄₈H₅₂Cd₂N₈O₂₂V₄ (1), triclinic. a=10.3366(10), b=11.320(3), c=13.268(3) Å, =103.888(17)°, β=92.256(15)°, γ=107.444(14)°, Z=1; C₇₂H₁₃₁N₁₂Ni₂O_29.5V₄ (2), triclinic. a=12.305(3), b=13.172(6), c=15.133(4), =79.05(3)°, β=76.09(2)°, γ=74.66(3)°, Z=1. Data were collected on a Siemens P4 four-circle diffractometer at 293 K in the range 1.59° <θ<26.02° and 2.01°<θ<25.01° using the ω-scan technique, respectively. The structure of 1 consists of a [V₄O₁₂]⁴⁻ cluster covalently attached to two {Cd(phen)₂}²⁺ fragments, in which the [V₄O₁₂]⁴⁻ cluster adopts a chair-like configuration. In the structure of 2, the [V₄O₁₂]⁴⁻ cluster is isolated. And the complex formed a layer structure via hydrogen bonds between the [V₄O₁₂]⁴⁻ unit and crystallization water molecules.     

乙二胺三乙酸与锌(Ⅱ)、钴(Ⅱ)相互作用的固体和溶液化学特性

在水热和弱酸性反应条件下,螯合型表面活性剂前驱体乙二胺三乙酸分别与氯化锌、氯化钴反应,形成水合乙二胺三乙酸金属配合物[M(H₂O)₆][M(ED3A)(H₂O)]₂·2H₂O[M=Zn(1),Co(2);H₃ED3A=乙二胺三乙酸,C₈H₁₄N₂O₆]。 产物经元素分析、红外、热重、液体核磁共振和X射线单晶衍射结构表征。 乙二胺三乙酸和锌(Ⅱ)、钴(Ⅱ)五配位,并与水一起形成典型的[MN₂O₄]或[MO₆]八面体结构。 ¹³C核磁共振实验结果表明,溶液中乙二胺三乙酸与锌形成配合物在弱酸性条件下(pH值3~7)稳定存在,在酸性溶液中完全解离,乙二胺三乙酸进一步经分子内成环反应生成3-酮哌嗪二乙酸(H₂kpda=C₈H₁₂N₂O₅)。     

One Dimensional Iron Molybdophosphate Anionic Chains with Different Structural Arrangements Reflecting a Flexibility Character

Structural comparison of a new compound[(bpp)₃H₆]Fe₂^IIIFe₂^IIMo₂₄^V(H₂PO₄)₈(HPO₄)₄(PO₄)₄O₄₈(OH)₁₂· (H₂O)₄·2H₂O(1)[bpp=1,3-di(4-pyridyl)propane] with our previously reported two compounds[(bpy)₃Fe^II]₃· Fe₂^IIIFe₂^IIMo₂₄^V(H₂PO₄)₈(HPO₄)₄(PO₄)₄O₄₈(OH)₁₂(H₂O)₄·12H₂O(2) and[(bpy)₃Fe^II]₂Fe^IIFe^IIIMo₁₂^V(H₂PO₄)₂(H_2-xPO₄)·(H_1+xPO₄)(HPO₄)₂(PO₄)₂O₂₄(OH)₆(H₂O)₂·9H₂O(x=0―1)(3)(bpy=2,2'-bipyridine), which all exhibit one-dimensional mixed-valence iron molybdophosphate anionic chains constructed by alternating connection of Fe^III ions and magic[Fe^II(Mo₆P₄O₃₁)₂] units, reveals that the non-hydrogen atomic ratios of Mo:Fe:P:O within the polymeric anionic chains are the same for all the three compounds, while the polymeric anionic chains of the different compounds bear different numbers of negative charges. And therefore there exist different numbers of counter cations per {Fe₂^III[Fe₂^II(P₁₆Mo₂₄^VO₁₂₄)]} unit found in the titled compounds. It discloses that not only are the spatial assembling of counter cations and polymeric inorganic chains of three compounds quite different, but also the O―Fe^III―O bond angles and Fe^III―O bond lengths of the three different inorganic chains exhibit small differences. What is more important is that such small changes in bond length and bond angle in the assemblage of Fe^III―O bonds lead to the considerable fluctuations of inorganic chains in their structural conformation within the three compounds, reflecting an interesting phenomenon of “flexibility" in the pure inorganic one dimensional mixed-valence iron molybdophosphate chains.     

X-ray crystal structure and vibrational spectra of hydrazides and their metal complexes. Part II. Hexaaquacobalt(II)bis(phthalhydrazidato)tetrahydrate

The hexaaquacobalt(II)bis(phthalhydrazidato)tetrahydrate, [Co(H₂O)₆](C₈N₂O₂H₅)₂·4H₂O is examined using single crystal X-ray diffraction analysis. The crystals are triclinic, space group , with a = 9.757(1), b = 10.955(2), c = 11.106(1),  = 100.79(2), β = 90.35(3), γ = 91.54(1) and Z = 2. In [Co(H₂O)₆](C₈N₂O₂H₅)₂·4H₂O, the cobalt(II) is coordinated by six water ligands and the [Co(H₂O)₆]²⁺ is associated with the two O-deprotonated phthalhydrazidato ions only by hydrogen bonds. The infrared and Raman spectra of phthalhydrazide (PH) and infrared spectra of deuterated derivative phthalhydrazide (PD) and of [Co(H₂O)₆](C₈N₂O₂H₅)₂·4H₂O are reported. The theoretical wavenumbers, infrared intensities and Raman scattering activities have been calculated using density functional (B3LYP) method with the 6-311++G(d,p) basis set. The calculated potential energy distribution has proved to be of great help in assigning the spectra PH, its deuterated derivative and [Co(H₂O)₆](C₈N₂O₂H₅)₂·4H₂O. The results from natural bond orbital (NBO) analysis for keto-hydroxy form of PH are presented.     

A spectroscopic study on the reaction-controlled phase transfer catalyst in the epoxidation of cyclohexene

The epoxidation of cyclohexene with hydrogen peroxide in a biphase medium (H₂O/CHCl₃) was carried out with the reaction-controlled phase transfer catalyst composed of quaternary ammonium heteropolyoxotungstates [π-C₅H₅N(CH₂)₁₅CH₃]₃[PW₄O₁₆]. A conversion of about 90% and a selectivity of over 90% were obtained for epoxidation of cyclohexene on the catalyst. The fresh catalyst, the catalyst under reaction conditions and the used catalysts were characterized by FT-IR, Raman and ³¹P NMR spectroscopy. It appears that the insoluble catalyst could degrade into smaller species, [(PO₄){WO(O₂)₂}₄]³⁻, [(PO₄){WO(O₂)₂}₂{WO(O₂)₂(H₂O)}]³⁻, and [(PO₃(OH)){WO(O₂)₂}₂]²⁻ after the reaction with hydrogen peroxide and becomes soluble in the CHCl₃ solvent. The active oxygen in the [W₂O₂(O₂)₄] structure unit of these soluble species reacts with olefins to form the epoxides and consequently the corresponding W---Ob---W (corner-sharing) and W---Oc---W (edge-sharing) bonds are formed. The peroxo group [W₂O₂(O₂)₄] can be regenerated when the W---Ob---W and W---Oc---W bonds react with hydrogen peroxide again. These soluble species lose active oxygen and then polymerize into larger compounds with the W---Ob---W and W---Oc---W bonds and then precipitate from the reaction solution after the hydrogen peroxide is consumed up. Part of the used catalyst seems to form more stable compounds with Keggin structure under the reaction conditions.     

Metallorganische lewissäuren : XX. Reaktionen von (π-C5H5)(CO)2LM-X (L = CO, PR3; M = Mo, W; X = BF4, PF6, AsF6, SbF6) mit Schwefel-haltigen liganden

The compounds (π-C₅H₅)(CO)₂LM-X (L = CO, PR₃; M = Mo, W; X = BF₄, PF₆, AsF₆, SbF₆) react with H₂S, p-MeC₆H₄SH, Ph₂S and Ph₂SO(L′) to give ionic complexes [(π-C₅H₅)(CO)₂LML′]⁺ X⁻. Also sulfur-bridged complexes, [(π-C₅H₅)(CO)₃W---SH---W(CO)₃(π-C₅H₅)]⁺ AsF₆⁻ and [(π-C₅H₅)(CO)₃M-μ-S₂C=NCH₂Ph-M(CO)₃(π-C₅H₅)], have been obtained. Reactions with SO₂ and CS₂ have been examined.     

Synthesis and structure of a novel molybdenum imido calix[6]arene

Treatment of p-tert-butylcalix[6]areneH₆ (H₆L) with [Mo(OBu^t)₂{[2,2′-(N)-C₆H₄]₂(CH₂CH₂)}] in refluxing toluene affords, after work-up, the complex [Mo(2-NC₆H₄CH₂CH₂C₆H₄NHC(Me)NH-2^/)LH₂]·4MeCN (1), which contains an 11-membered metallocyclic ring as characterised by Synchrotron X-radiation.     

Degradation Method for Preparing Organo-Arsenic and-Antimony Polytungstates and Comparative Study of Corresponding Polymolybdates

In repeating and extending the syntheses of organo-arsenic polytungstates,we found that the "Degradation Method",taking sodium metatungstate as the starting material,was much more profita-ble.The known compound (CN3H6)5[(C6H5As)2W6O25H]2H2O(1) was read-ily reproduced with a high yield.A new compound (CN3H6)6[(p-OH,m-NO2C6H3As)2W6O25](2) was likewise synthesized.This "Degradation Method" using the reaction of sodium metatungstate with organo-anti-monate led to the isolation of four compounds with definite composition although amorphous in appearance.The preparations of organo-arsenic polymolybdates and organo-antimony polymolybdates were also studied and six new organo-arsenic polymolybdates were isolated: (CN3H6)5[(C6H5As)2MoO25H]H2O(3),(CN3H6)4[(n-C3H7As)2Mo5O21]2H O (4),(CNH)4[(n-C3H7As)2Mo6O24](5),Cs2[(CH3)2AsMo4O15H](6),相似文献   

A localized molecular orbital study on the bonding of> Mo3S4]2Mo> and> Mo3S4]CuI> versus (C6H6)2Cr and C6H6Cr(CO)3

The energy-localized CNDO/2 molecular orbitais have been calculated for the clusters containing molybdenum, > {Mo₃S₄₂Mo}⁸⁺ and> Mo₃S₄]CuI> ⁴⁺, versus the prototype arene-metal sandwich (C₆H₆)₂Cr and half-sandwich complexes C₆H₆Cr(CO)₃. The bonding characteristics of these compounds are described from a localization bonding viewpoint. There are two typical M-arene and M-[Mo₃S₄] bondings. One is formed by electron donation from the three-center two-electron π-bonds in the arene or [Mo₃S₄]⁴⁺ ligands into the vacant hybrid orbitais of the “stranger” metal atom. In the other M-arene or M-[Mo₃S₄] bond there is very little donation by the lone electron pair occupying the d AOs of the “stranger” metal atom to the arene or [Mo₃S₄]⁴⁺ ligands. The analogy of the ligand [Mo₃S₄]⁴⁺ in the clusters studied with the ligand benzene is also briefly discussed.     

一个钼钒二聚体簇合物的合成及其性能

以NH₄VO₃, H₃PMo₁₂O₄₀·xH₂O, Cu(NO₃)₂和哌嗪为主要原料,采用水热方法,合成了一个新的钼钒二聚体簇合物--(H₂NC₄H₈NH₂)₆［Mo^VI₁₆V^V₁₂P₂O₈₄］·5H₂O(1),其结构和性能经UV-Vis, IR, X-射线衍射、光电子能谱及热重分析表征。1属单斜晶系,P2(1)/c空间群, 晶胞参数a=20.450(4) , b=24.989(5) , c=20.450(4) , β=93.89 °, V=10 427(4) ³, Fw=4 159.18, Dc=2.650 g·cm^-3, μ=3.018 mm^-1, F(000)=7 952, Gof=1.029。晶体结构解析表明：1由两个单元Keggin型簇核［PMo₈V₆O₄₂］^7-聚合而成一个二聚体簇［P₂Mo_l6V₁₂O₈₄］^14-,该二聚体簇核和有机配体哌嗪之间通过复杂的氢键相互作用,展示三维超分子网络结构。     

New Supramolecular Networks Based on Paratungstate with N-Donor Bridging Ligands

Three new supramolecular networks based on paratungstate and N-donor bridging ligands, [H₂bpmp]_2.5H[H₂W₁₂O₄₀]2H₂O(1), [H₂(bpp)]₂[H(py―CH₃)]_0.25[H(py―C₂H₅)]_0.25H_1.5[H₂W₁₂O₄₀]·4H₂O(2) and [H₂pip]₃[H₂W₁₂O₄₀](3)[bpmp=N,N'-bis(4-pyridylmethyl)piperazine; bpp=1,3-bis(4-pyridyl)propane; py=pyridine; pip=piperazine] were prepared by the hydrothermal synthesis and characterized by elemental analysis, infrared(IR), thermogravimetric(TG) analysis and single-crystal X-ray diffraction(XRD). All the compounds show high-dimen- sional supramolecular networks based on [H₂W₁₂O₄₀]^6- and the protonated N-donor ligands via the N―H···O―W hydrogen bonds and/or π···π stacking interactions. Their luminescent properties were investigated.