Synthesis,Crystal Structure of Cis—dioxo—catecholatotungsten（VI） Complex and Its NMR Studies on the Interaction with ATP

Cis-dioxo-catecholatotungsten(VI) complex anion[W^(VI)O2-(OC6H4O)2]^2- was obtained with discrete protonated ethylenediamine (NH2CH2CH2NH3)^ cations by the reaction of tetrabutyl ammonium decatungstate with catechol in the mixed solvent of CH3OH,CH3CN and ethylenediamine,and compared with its molybdenum anaogue [Mo^(V) O2(OC6H4O)2]^3- by crystal structure,UV,EPR,The results of the UV and EPR spectra show that tungsten is less redox active than molybdenum since the molybdenum is reduced from Mo(VI) to Mo(V) but tungsten stays in the original highest oxidized state Mo(VI) when they are crystallized from the solution above.It is worthy to note that [W^(VI)O2(OC6H4O)]^2- shows the same coordination structure as its molybdenum analogue in which the metal center exhibits distorted octahedral coordination geometry with two cis-dioxocatecholate ligands and might have the related coordination structure feature with the cofactor of flavoenzyme because [Mo^(V)O2(OC6H4O)2]^3- presented essentially the same EPR spectra as flavoenzyme.The NMR studies on the interaction of the title complex with ATP reveal that the reduction of W(VI) to W(V) occurs when the title complex is dissolved in D2O and the W(V) is oxidized again when ATP solution is mixed with original solution and the hydrolysis of the catecholato ligand take places at mean time being monitored by ^1H NMR and ^13C NMR spectra.     

Interactions with ATP, DNA Cleavage and Anti-tumor Activities of Complexes with Anions [Mo（V）O2（O2CeH4）2]^3-, [Mo（Ⅴ）0.5W（Ⅵ）0.5O2（O2C6H4）2]^2.5- and [W（Ⅵ）O2（O2C6H4）2]^2-

(NH3CH2CH2NH2)3[Mo(Ⅴ)O2(O2C6H4)2] (1), (NH3CH2CH2NH2)2.5[Mo(Ⅴ)o.sW(Ⅵ)o.502(O2C6H4)2] (2) and(NH3CH2CH2NH2)2[VC(Ⅵ)O2(O2C6H4)2] (3) were synthesized, structurally characterized by X-ray diffraction analysis, and studied on their interactions with ATP, their DNA cleavage activities and antitumor properties. The redox state of molybdenum was not changed on going from crystal to aqueous solutions in complexes 1 and 2, while tungsten underwent reduction from W(VI) to W(V) in complexes 2 and 3. ATP promoted the oxidation of both molybdenum and tungsten from M(Ⅴ) to M(Ⅵ) and the hydrolysis of catecholate ligands in solution consisting of ATP and the complexes. Complex 1 possesses fairly good activity to DNA cleavage and against tumor S180 in mice, and is more effective than the control drug cyclophosphamide under the identical conditions. However, complexes 2 and 3 exhibited marginal effectiveness. The effectiveness of anti-tumor of the complexes was related positively to their DNA cleavage activities and their hydrolysis of catecholate ligands.     

Macro-, Micro-, Nano- and Crystal Structures of a Homodinuclear Complex [NH3（ CH2）3NH3]2{Na2[（C6H4O2）2]（C6H4O2H）2}

A homodinuclear complex （NH3CH2CH2CH2NH3）2 {Na2[（C6H4O2）2] （C6H4O2H）2} （1） has been synthesized by a solution-based self-assembly route. It crystallized in monoclinic system with space group P21/c. Every sodium ion coordinates in a tetragonal prism fashion with two O atoms of a terminal chelating catecholate ligand and three O atoms from two bridging catecholate ligands. Two neighboring NaO5 tetragonal prisms are edge-shared and centrosymmetric with regard to the inversion center to form a binuclear cluster {Na2[（C6H4O2）2]（C6H4OOH）2}^4- anion. The complex anions were aligned parallelly by n-n interaction and linked with the protonated 1,3-propylenediamine through hydrogen bonds which were assembled into a multi-lamellar structure with channels. The crystal exhibits rectangular geometry with an interior triangle hollow structure under optical microscopy. And the scanning electron microscopy （SEM） indicates that the wall of the tubes shows multi-lamella morphologies. Further, the transmission electron microscopy （TEM） reveals that the crystal is composed of multi-lamellar nano-tubes with diameters less than 100 nm. The molecular structure of the complex was compared with that of its isomer complex 2.     

The Reaction of Molybdenum with 2,3-Dihydroxynaphthalene

[H2N（CH2）3NH312[MoO2（C10H6O2）2] （1） was synthesized by the 2,3-dihydroxynaphthalene in the mixed solvent of CH3OH, CH3CN reaction of （n-Bu4N）4[Mo8O26] with and 1,3-propanediarnine. （C5HllN2）2- [HeN（CH2）3NH2][MoO2（CloH6O2）2] （2） was obtained by the reaction of Na2MoO4.2H20 with 2,3-dihydroxynaphthalene in the same solvent above. Both of the complexes possess complex anion [Mo（VI）O2（OC10H6O）2]^2- which shows pseudo-octahedrally coordinated fashion, while the counterions are two protonated 1,3-propanediamine in complex 1 and （CsH11N2）^＋ in complex 2. （C5H11N2）＋ is the byproduct of reaction 2, which results from combination of acetonitrile with 1,3-propanediamine. Packing diagrams of the two complexes are also different. There is anti-parallel-aligned-double-meso-bilayer unit in complex 1. However there are four chiral anions arranged in anticlockwise orientation in complex 2.     

Synthesis and Structure of Bis（indene—1,2,3—trione 2—oximato）bis （aqua）Mn（Ⅱ）：Mn（C9H4NO3）2（H2O）2

1 INTRODUCTION The interest in the complexes of transition metals with ligands ketoxime[1, 2] as potential models for metal binding sites in ferroverdin[3, 4] has prompted the investigation on the structures and the overall coordination geometry of the metal centers in these complexes. Oxime derivatives are interesting ligands since the ketoximes are found to chelate transition metals through the N (oxime) and O (ketone) atoms[5, 6]. However, monodentate coordination via only one O or …     

Theoretical Investigations on the Interaction Nature of Br2 with HF, H2O and NH3

The interactions of HF, H2O and NH3 with Br2 are investigated at the MP2(full)/ aug-cc-pVDZ level. It is found that two kinds of stable complexes, halogen-bonded and hydrogen- bonded complexes, exist between Br2 and HF and between Br2 and H2O. The interaction energy analysis and natural population analysis (NPA) are conducted to these two kinds of complexes, indicating the halogen-bonded complexes are more stable than the corresponding hydrogen-bonded ones, and the binding energies of the former increase in the order HFH2O for the latter.     

Synthesis, Crystal Structure and Properties of Complex VO（C10H9NO3） （C13H10NO2）

Complex VO(C10H9NO3)(C13H10NO2)(C10H9NO2-3=N-salicylidene-L-alaninate, C13H10NO-2=N-phenylbenzohydroxamate) was synthesized and characterized by means of elemental analysis, IR, UV, 1H NMR spectroscopies, cyclic voltammetry and single crystal X-ray diffraction. The complex crystallized in a monoclinic system with space group P21 and crystal cell parameters a=0.9720(1) nm, b=1.8274(2) nm, c=1.2542(1) nm, β=104.868(9)°, V=2.1532(4) nm3, Mr=470.34, Z=2. The two oxygen atoms and the one nitrogen atom of the tridentate Schiff base ligand and the one oxime oxygen atom of the hydroxamate ligand coordinate to the vanadium atom, forming an equatorial plane, the two axial positions are respectively occupied by the oxygen atom of the oxovanadium and the carbonyl oxygen atom of the hydroxamate and the vanadium atom exhibits a distorted octahedral VO(ONO)(OO) coordination sphere. The 1H NMR spectrum suggests that the two isomers, endo and exo in a molar ratio of 1/1.7, coexist in the solution of the title complex in CDCl3. There exists a quasi-reversible one-electron redox reaction corresponding to VⅤ/VⅥ couple in the three non-aqueous solvents, and the redox potential E1/2 of the title complex substantially shifts in the direction of the positive voltage increase in the order: CH2Cl2＜CH3CN＜DMF.     

Crystal Structure, Nano-particle Morphology and Interaction with ATP of [ NH3 CH2 CH（ NH2 ） CH3 ]2 [ M（ Ⅵ ） O2 （ OC6 H4 O）2 ] （M = Mo0. 6 W0. 4 ） and Its Activity to Promote DNA Cleavage

The title complex [NH_3CH_2CH(NH_2)CH_3]_2 [M(Ⅵ)O_2(OC_6H_4O)_2](M= Mo_(0.6)W_(0.4))was synthesized via a simple solution-phase chemical route.The determination of single crystal X-ray diffraction revealed that the title compound is crystallized in a monoclinic system with P2(1)/n space group,a=1.0913(10)nm,b=1.0442(10)nm,c=1.8842(19)nm,α=90°,β=96.530(17)°,γ=90°,Z=4,and V=2.133(4)nm3.The mononuclear anionic unit [M(Ⅵ)O2(OC6H4O)2]2-displays chiral pseudo-octahedral [MO_6] coordination geometry and is linked by chiral cations via hydrogen bond and π…π stacking interaction.The transmission electron microscopy images show that the title complex is comprised of nano-particles with diameters ranging from 20 to 50 nm.The NMR study shows the 1H downfield chemical shifts of [NH_3CHaHbCH(NH_2)CH_3] cations in the title complex when it is mixed with adenosine-triphosphate(ATP),and the chemical shift difference between Ha and Hb is increased greatly,and most of the catecholate ligands dissociate from the central metal atoms.The DNA cleavage activity experiment reveals that DNA cleavage promoted by the title complex is lower than that by Na_2MoO_4 which possesses antitumor pro-perty,but higher than that by Na_2WO_4.     

Crystal Structure,Electrochemical and Fluorescent Properties of a New Cadmium（II） Complex [Cd（C12H6O4N2）（Phen）2（H2O）]·3H2O

A new Cd（II） complex [Cd（C12H6OaN2）（Phen）ffH2O）]＇3H2O with 2,2＂-bipyridine- 3,3＂-dicarboxylic acid as a ligand has been synthesized. Crystal data for the title complex are as follows： monoclinic, space group P2dn, a = 12.8458（5）, b = 17.9131（7）, c = 15.2960（6） A, β = 111.7430（10）°, V = 3269.3（2） A3, Dc = 1.581 g/cm3, Z = 4,/a（MoKa） = 0.731 mm-1, F（000） = 1580, the R = 0.0244 and wR = 0.0605. In the title complex, the central Cd（ll） ion is located in a distorted octahedral coordination environment. The electrochemical and fluorescent properties of the title complex were studied. The results show that the electron transfer of the title complex is irreversible in the electrode reaction and it has a broad emission peak in the range of 470-508 nm with the excitation wavelength of 488 nm.     

Synthesis, Crystal Structure and Characterization of α-（1-Benzimidazolyl） -hypnone Cobalt（Ⅱ） Complex： [CoCl （ C7H5N2CH2COPh）4] Br

The crystal structure of [CoCl ( C7H5N2CH2COPh)4] Br has been determined by means of X-ray crystallography. The molecular structure consists of a discrete [CoCl ( C7H5N2CH2COPh)4] ^ cation and one Br^- anion, in the [CoCl ( C7H5N2CH2COPh)4]^ cation, the coordination geometry of the central Co atom is square-pyramidal with four tertiary N atoms of benzimidazole from four α-( benzimidazol-1-yl) -hypnone ligands in the basal position and one chloride anion in the apical position. In the solid state, [CoCl ( C7H5N2CH2COPh)4]^ and Br^- anion possess intermolecular and intramolecular interactions, which stabilize the crystal structure. The characterization of the title compound were also carried out by using elemeutal analysis, FTIR, UV spectrometries and TG-DSC.     

Structures that should be Described in Higher-Symmetry, Centrosymmetric Space Groups. Part 2. The Structures of [Ni(C_5H_4NO-2-CH=N-CH_2CH_2-N=CH-2-C_5H_4NO)(H_2O)_2]- (ClO_4)_2, {Ni[C_5H_4NO-2-CH=N-CH(CH_3)CH_2-N=CH-2- C_5H_4NO](H_2O)_2}

1　ＩＮＴＲＯＤＵＣＴＩＯＮＳｅｖｅｒａｌｉｎｃｏｒｒｅｃｔｓｐａｃｅｇｒｏｕｐｓｈａｖｅｂｅｅｎｒｅ ａｓｓｉｇｎｅｄｂｙｍａｋｉｎｇｕｓｅｏｆｓｉｍｕｌａｔｅｄｓｔｒｕｃｔｕｒｅｆａｃｔｏｒｓ;ｈｏｗｅｖｅｒ,ｔｈｅｃｒｕｘｏｆｔｈｉｓｏｒａｎｙｓｐａｃｅｇｒｏｕｐｒｅｖｉｓｉｏｎｉｓｔｈｅａｃｃｕｒａｔｅｒｅｐｏｒｔｉｎｇｏｆｔｈｅｓｐａｃｅｇｒｏｕｐａｎｄａｔｏｍｉｃｃｏｏｒｄｉｎａｔｅｓｏｆｔｈｅｉｎｃｏｒｒｅｃｔｌｙｄｅｔｅｒｍｉｎｅｄｓｔｒｕｃｔｕｒｅｓｉｎｃｅｔｈｅｔｒｕｅｓｔｒｕｃ…     

新型环形聚阴离子[{WO(H_2O)}_3(AsW_8O31)_3]~21-的结构及表征

在pH=3.0的水溶液中，Na_2WO_4·2H_2O与NaAsO_2·6H_2O和NH_4Cl反应，得 到了新的杂多钨酸盐(MH_4)_19Na_2[{WO(H_2O)}_3(AsW_8O31)_3]·45H_2O单晶， 用X射线单晶衍射法及元素分析确定了其结构，晶体属单斜晶系，空间群C2/c，晶 胞参数为：a=3.1165(11)nm, b=1.7388(7)nm, c=2.2789(9)nm, β=97.342(6)°, V=12.248(8)nm~3, Z=4, R_1=0.0571,wR_2=0.0741[I＞2σ(I)]. 环型聚阴离子 [{WO(H_2O)}_3(AsW_8O31)_3]~21-是由三个{WO(H_2O)}桥连三个新发现的 {AsW_8O31}单元构成的，环聚离子[{WO(H_2O)}_3(AsW_8O31)_3]~21-具有近似D_ (3h)对称性。对该化合物还进行了~183W NMR, IR和TG表征。     

Synthesis and Crystal Structure of［（n－Bu）_4N］_2［Mo_4O_（10）（OC_（10）H_6O）_2（OCH_3）_2］

ＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ［（ｎ－Ｂｕ）_４Ｎ］_２［Ｍｏ_４Ｏ_（１０）（ＯＣ_（１０）Ｈ_６Ｏ）_２（ＯＣＨ_３）_２］￥ＬｕＸｉａｏ－Ｍｉｎｇ；ＺｈｕＨｕｉ－Ｊｕ；ＹａｎｇＮｉｎｇ；ＬｉｕＳｈｕｎ－Ｃｈｅｎｇ；ＪｉｎＸ?..     

Synthesis and Structureof［（C_2H_5）_4N］［Mo_3（μ_3－O）（μ－Cl）_3（μ－CH_3CH_2COO）_3Cl_3］

ＳｙｎｔｈｅｓｉｓａｎｄＳｔｒｕｃｔｕｒｅｏｆ［（Ｃ_２Ｈ_５）_４Ｎ］［Ｍｏ_３（μ_３－Ｏ）（μ－Ｃｌ）_３（μ－ＣＨ_３ＣＨ_２ＣＯＯ）_３Ｃｌ_３］ＺｈｕａｎｇＨｏｎｇ－Ｈｕｉ；ＷｕＤｉｎｇ－Ｍｉｎｇ；ＨｕａｎｇＪｉａｎ－Ｑｕａｎ；ＨｕａｎｇＪｉｎ－Ｌ...     

Synthesis and Crystal Structure of［Na（DB18C6）（H_2O）_2］_2Mo_6O_（19）·3DMF·2CH_3OH

ＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ［Ｎａ（ＤＢ１８Ｃ６）（Ｈ_２Ｏ）_２］_２Ｍｏ_６Ｏ_（１９）·３ＤＭＦ·２ＣＨ_３ＯＨＬｕＸｉａｏ－Ｍｉｎｇ；ＺｈａｏＹａ－Ｐｉｎｇ；ＱｕＥｒ－Ｌｉｎｇ；ＸｉａｏＬｉｎｇ－Ｍｅｉ；ＬｉｕＳｈｕ...     

六核钴羰基簇的P(OC_2H_5)_3取代衍生物的合成、表征与结构

用P(OC_2H_5)_3与母体簇Co_6(μ_6-P)(μ-SCH_2CH_2CH_2S)(μ- PSCH_2CH_2CH_2S)(CO)_(12)进行取代反应得到一个二取代产物Co_6(μ_6-P)(μ- SCH_2CH_2CH_2S)(μ-PSCH_2CH_2CH_2S)(μ-CO)(CO)_9[P(OC_2H_5)_2]_2（I）, 同时还得到了两个一取代产物Co_6(μ_6-P)(μ-SCH_2CH_2CH_2S)(μ- PSCH_2CH_2CH_2S)(CO)_(11)[P(OC_2H_5)_3]（II a和II b,II b是II a的一个同 分异构体,其谱学数据与II a不同）。对合成的三个簇合物进行了元素分析、IR、 ~1H NMR、~(31)P NMR和MS谱学表征,对I做了X射线单晶衍射测定,其晶体属于单 斜晶系,P2_1/n空间群,晶胞参数：a = 1.1170(2) nm,b = 2.3554(5) nm,c = 1.7977(4) nm,β = 99.50(3)°,V = 4.6649(17) nm~3,Z = 4,D_c = 1.763 g/cm~3,F(000) = 2488,μ = 24.64 cm~(-1)。X射线晶体结构分析表明,取代 位置发生在簇合物顶端的两个钴原子上。晶体结构用直接法解出,经用全矩阵最小 二乘法对原子参数进行修正,最后的偏离因子为R_1 = 0.0497,wR_2 = 0.1386。     

(enH_2)_5[(VO)_(12)O_6B_(18)O_(36)(OH)_6]·2(H_3O)·6H_2O的水热合成和晶体结构

以NH4VO3,H3BO3,乙二胺,MoO3,H2O为原料,按物质的量比2∶20∶9∶3∶222,在180℃条件下晶化,得到黑色棱形晶体(enH2)5[(VO)12O6B18O36(OH)6].2(H3O).6H2O.单晶结构分析结果表明该化合物属三斜晶系,Pī空间群,晶胞参数a=1.336 8(3)nm,b=1.599 8(3)nm,c=1.663 4(3)nm,α=94.040(1)°,β=91.530(1)°,γ=95.830(1)°,V=3.528 1(12)nm3,Z=2,Dc=2.099 g/cm3,μ=1.649 mm-1,F(000)=2 228,15 641个可观察独立衍射点射点(I>2σ(I)),最后结构精修到偏离因子R1=0.047 5,wR2=0.150 4,S=1.039.该化合物的结构主要由阴离子簇[(VO)12O6B18O36(OH)6]12-构成.该阴离子簇由B18O36(OH)6十八元环夹在两个以共边交替相连形成的V6O18簇中间,通过共用氧原子形成三明治式结构新颖的硼-钒-氧离子簇,簇间填充了一些(enH2)2+离子和水分子.     

钛酸丁酯与酐的反应和产物钛氧有机化合物结构分析

钛酯丁酯与乙酐在环已烷中混合加热反应，钛酸丁酯中的烷氧基容易发生二取 代反应，生成溶于有机溶剂的丁氧基乙酸钛和乙酸丁酯；在过量的乙酐存在下，二 取代产生形成两种不同结构的钛氧有机物，乙酸氧钛和丁氧基乙酸氧钛，两种物质 分子中都存在Ti-O-Ti键型的结构，它们不溶于有机溶剂。Ti_2O(OC_4H_9)_2 (OOCCH_3)_4更容易加热分解。     

(NH_4)_(42)[Mo_(132)O_(372)(CH_3COO)_(30)(H_2O)_(72)]膜修饰电极的构筑和电化学性质的研究

由于过渡金属替代的多金属氧酸盐(polyoxometalates)的催化、磁性、电化学等性质,越来越受到人们的关注~([1-7]). 目前世界上约有10亿人生活在缺碘地区,碘的缺乏严重影响人类健康.对食物、生物临床、环境及工业中碘含量检测很有实际意义.