新型负载配位催化剂ZBDPPEDAEPA／TiO2／Pd催化羰化反应研究

用乙二胺-N'-乙基膦酸的氨基与季盐[Ph2P+(CH2OH)2]Cl-,经曼尼希反应合成了N,N-双二苯膦甲基-乙二胺-N'-乙基膦酸(Ph2PCH2)2NCH2CH2N+H2CH2CH2PO3H-(BDPPEDAEPA), 并制备了相应的(N,N-双二苯膦甲基-乙二胺-N'-乙基膦酸-磷酸氢)锆载体Zr(HPO4)1.35[(Ph2PCH2)2NCH2CH2NHCH2CH2PO3]0.65·H2O (ZBDPPEDAEPA) 及二氧化钛和二氧化锆微粉表面包膜了ZBDPPEDAEPA的新型催化剂载体ZBDPPEDAEPA / TiO2、ZBDPPEDAEPA/ ZrO2和相应的钯催化剂ZBDPPEDAEPA / Pd、ZBDPPEDAEPA / TiO2 / Pd、ZBDPPEDAEPA/ZrO2/Pd. 在常压条件下, 对该类催化剂催化氯苄羰化反应的活性及产物组成作了初步考察. 对催化剂载体的粒径分析表明, ZBDPPEDAEPA / TiO2 / Pd的高活性归因于ZBDPPEDAEPA / TiO2载体的颗粒均匀、平均粒径小.ZBDPPEDAEPA以平均50 nm的薄层包膜在TiO2上, 这层包膜属于纳米级催化材料.     

[(N-膦酸亚甲基)亚氨基二乙酸-亚磷酸氢]锆一钯催化剂的催化加氢活性

一类新型负载钯催化剂：〔（N-膦酸亚甲基）亚氨基二乙酸-亚磷酸氢〕锆-钯催化剂由Zr（HPO3）2-x〔O3PCH2N（CH2CO2H）2〕x·H2O与Pd－Cl2在无水乙醇中络合制得。用IR，XPS谱对该催化剂进行了表征，并研究了催化剂的X值，钯含量，＞NCH2CO2H／Pd摩尔比，反应温度，PH值，溶剂和底物对加氢活性的影响。催化剂重复使用8次而无显著失活。     

晶态层状(甘氨酸-N，N-双亚甲基膦酸-磷酸氢)锆的制备和插层

晶态层状(甘氨酸-N;N-双亚甲基膦酸-磷酸氢)锆的制备和插层;（甘氨酸-N;N-双亚甲基膦酸-磷酸氢）锆; 正丁胺; 插层     

N,N''''-(2-苯并咪唑基甲基)亚氨基甲基膦酸的双核镍化合物Ni2(bbimp)2(4,4''''-bipy)(H2O)2·2H2O和Ni2(bbimp)2(H2O)2][Ni(bbimp)(H2O)2]2·4H2O的晶体结构和磁学性质

该文报道了N,N′-(2-苯并咪唑基甲基)亚氨基甲基膦酸{bbimpH_2,[(C7H5N2)CH2]2NCH2PO3H2}的2个镍化合物Ni2(bbimp)2(4,4′-bipy)(H2O)2·2H2O(1)和[Ni2(bbimp)2(H2O)2][Ni(bbimp)(H2O)2]2·4H2O(2)。化合物1是4,4′-联吡啶作为桥连配体的中性双核结构。化合物2含有1个中性的[Ni2(bbimp)2(H2O)2]双核分子与2个中性的[Ni(bbimp)(H2O)2]单核分子。双核分子单元中的2个Ni!离子被2个膦酸氧桥连。在化合物2中,膦酸氧桥连的2个Ni!离子之间存在铁磁性相互作用。     

新型磷-钒-氧层状化合物[H2en]2[H3O]6[Co(H2O)2(VO)8(OH)4(PO4)8]的水热合成与晶体结构

金属磷酸盐材料在吸附、离子交换、离子传导和催化剂方面有潜在的应用前景[1～5]. 近年来, 通过水热反应合成了一些A-V-P-O化合物. 在这些化合物中, A一般为碱金属或有机阳离子, 如层状结构的[H2N(C4H8)2NH2][(VO)4(OH)4(PO4)2][6] 和[H2N(C2H4)3NH2][(VO)8(HPO4)3(PO4)4*(OH)2]*2H2O[6], 一维链状结构的 [H2NCH2CH2NH3(VO)(PO4)][7], 手性双螺旋结构的 [(CH3)2NH2]K4[(VO)10(H2O)2(OH)4(PO4)7]*H2O[8]以及具有三维骨架结构的化合物 [H3N(CH2)3NH3K(VO)3(PO4)3][9], [H3N(CH2)3NH3]2[V(H2O)2(VO)6(OH)2(HPO4)3(PO4)5]*3H2O[10]和[H3N(CH2)2NH3][(VO)3(H2O)2(PO4)2(HPO4)4][11].     

超分子碱金属膦酸盐——哌嗪双膦酸钠的合成及晶体结构

二维或三维金属膦酸盐聚合物作为功能材料在催化、离子交换和纳米材料等研究领域受到广泛关注 .最初的研究主要集中在四价金属盐 ,后来陆续报道了对于其它价态金属盐的研究 [1～ 3] ,但关于单一碱金属的研究报道较少 . 2 0 0 0年 ,Aranda等[4 ] 报道了首例 Na2 [( HO3PCH2 ) 3NH ]· 1 .5 H2 O( Na PP- 1 )晶体结构 .与其它膦酸盐的明显差别是 ,碱金属双膦酸盐是治疗骨质疏松症的药物 [5] .本文从重要的医药原料哌嗪 [6 ]出发 ,制备并测定了一种具有超分子特征的 α-氨基双膦酸钠Na2 [( HO3PCH2 ) NC4 H8N( CH2 PO3H) ]( H2 O)…     

脂蛋白脂酶激活剂艾溴利平类似物的合成

合成了两个新型的艾溴利平类似物——N-2 -硝基-4-氯苯基-4-[(膦酸二乙酯基)甲基]苯甲酰肼(5,总收率28.1％)和N-2-四氮唑基-4-氯苯基-4-[(膦酸二乙酯基)甲基]苯甲酰胺(7,总收率30.5％).以对氯甲基苯甲酸为原料,经酯化、水解和酰氯反应制得中间体4-[(膦酸二乙酯基)甲基]苯甲酰氯(4);4与2-硝基-4-氯苯肼盐酸盐反应合成了5.4先与2-氨基-5-氯苯腈反应制得N-2-氰基-4-氯苯基-4-[(膦酸二乙酯基)甲基]苯甲酰胺(6);6再与叠氮化钠反应合成了7.其结构经1 H NMR和IR表征.     

配合物二乙基锡N-[(2-氧苯基)亚甲基]甘氨酸酯的合成、结构表征和生物活性

合成了5个新的二乙基锡N-[(2-氧苯基)亚甲基]甘氨酸酯(CH3CH2)2Sn(2-O-3-X-5-YC6H2CH=NCH2COO)(X,Y=H,H,1;H,Cl,2;H,Br,3;Cl,Cl,4;Br,Br,5),利用元素分析、IR、1H和129Sn NMR表征了其结构.通过X-射线单晶衍射测定了1和4的晶体结构.化合物1的晶体属单斜晶系,P21空间群;化合物4的晶体属三斜晶系,P1空间群.2个化合物均为由羧基桥联形成的[Sn3O6C3]十二元大环三聚体结构,锡原子的配位构型为六配位[SnC2NO3]畸变八面体.生物活性测试结果表明,化合物5对3种人癌细胞HeLa、CoLo205和MCF-7及大肠杆菌均有抑制活性.     

酸性化合物在十二胺-N,N-二亚甲基膦酸改性氧化锆固定相上的分离

酸性化合物在十二胺-N; N-二亚甲基膦酸改性氧化锆固定相上的分离;氧化锆;色谱固定相;十二胺-N; N-二亚甲基膦酸     

[NH3(CH2)5NH3][Fe2{O3PC(CH3)(OH)(PO3H)}2]@2H2O:一个新的二膦酸亚铁化合物的合成、结构与性质研究（英文）

通过水热合成得到一个新的有机二膦酸亚铁化合物[NH3(CH2)5NH3][Fe2Ⅱ(O3PC(CH3)(OH)(PO3H)}2]·2H2O,该化合物包含阴离子型共价双链[Fe2Ⅱ{O3PC(CH3)(OH)PO3H}2]n2n-,质子化的戊二胺和结晶水,双链之间通过强氢键构成一个开放型的骨架结构.另外,观察到亚铁离子之间存在弱铁磁性相互作用.     

手性膦酸锆的原位合成与表征

不对称催化和对映体拆分是有机化学中最活跃的高技术领域,其中手性固体材料的设计与合成是极具挑战性的前沿课题之一.据Corey等研究的手性技术机理,手性固体一般应该具有空间允许、手性源为官能化的有机化合物和金属离子作为反应的活性中心等三大特征．然而,迄今同时具有上述特征的手性固体材料却很少．     

High-throughput investigation and characterization of cobalt carboxy phosphonates

High-throughput methods have been employed to study the system Co(2+)/(H(2)O(3)PCH(2))(2)NCH(2)C(6)H(4)COOH/NaOH in detail. The use of the phosphonocarboxylic acid (H(2)O(3)PCH(2))(2)NCH(2)C(6)H(4)COOH has led to several new cobalt carboxyaryl phosphonates under hydrothermal conditions. In addition to the effect of the pH of the starting mixture, the influence of the counterions of the cobalt salts on the product formation was investigated. Thus, reaction trends as well as fields of formation could be identified. Four new compounds Co(2)[(O(3)PCH(2))(2)NCH(2)C(6)H(4)COOH].H(2)O (1), Co[(O(3)PCH(2))(OCH)NCH(2)C(6)H(4)COOH].H(2)O (2), Co[H(2)(O(3)PCH(2))(2)NCH(2)C(6)H(4)COOH] (3), and [Co(2)(O(3)PCH(2))(2)NCH(2)C(6)H(4)COOH].3.5H(2)O (4) were obtained, and compounds 1 and 2 could be isolated as single crystals suitable for single-crystal X-ray diffraction. The counterions of the cobalt salts have an influence on the structure of the resulting compounds. This is due to the effect on the initial pH as well as the possibility of the counterions to take part in redox reactions. Compounds 1 and 4 are formed under more basic conditions, and the phosphonic acid group is fully deprotonated. The structure of 1 is a rare example of the family of inorganic-organic hybrid materials with iminobis(methylphosphonic acid) units wherein the nitrogen coordinates to the metal center. Compound 2 is the result of an in situ oxidation of one of the P-C bonds; the organic building unit is stabilized by complexation of the cobalt ion. On the basis of spectroscopic, thermogravimetric, elemental chemical analysis, and EDX-analysis data, compound 3 has been characterized as Co[H(2)(O(3)PCH(2))(2)NCH(2)C(6)H(4)COOH] and compound 4 as [Co(2)(O(3)PCH(2))(2)NCH(2)C(6)H(4)COOH].3.5H(2)O. X-ray powder diffraction and IR-spectroscopic studies show that thermal treatment of 4 leads to the title compound 1. This transformation is accompanied by a change of color from pink to deep blue.     

油包水型微乳中层柱状磷酸锆的制备与表征

以氧氯化锆(ZrOCl2·8H2O)和磷酸三丁酯(C4H9O)3PO为原料, 在正庚烷(C7H10)-十六烷基三甲基溴化铵(CTAB)/正丁醇(C4H9OH)-水的反向微乳体系中制备了Zr(HPO4)2·H2O, (H3O)+Zr2(PO4)3和Zr(HPO4)8·H2O三种不同结构的层柱状磷酸锆. 运用扫描电子显微镜(SEM)、透射电子显微镜(TEM)和X射线衍射仪(XRD)等仪器对产物进行了表征, 考察了不同微乳组成对磷酸锆结构及尺寸的影响. 结果表明, 微乳体系对层柱状磷酸锆的可控制合成具有广泛意义.     

Synthesis and characterization of octa- and hexanuclear polyoxomolybdate wheels: role of the inorganic template and of the counterion

Eight new compounds based on [O3PCH2PO3]4- ligands and {MoV2O4} dimeric units have been synthesized and structurally characterized. Octanuclear wheels encapsulating various guests have been isolated with different counterions. With NH4+, a single wheel was obtained, as expected, with the planar CO32- guest, (NH4)12[(MoV2O4)4(O3PCH2PO3)4(CO3)2].24H2O (1a), while with the pyramidal SO32- guest, only the syn isomer (NH4)12[(MoV2O4)4(O3PCH2PO3)4(SO3)2].26H2O (2a) was characterized. The corresponding anti isomer was obtained with Na+ as counterions, Na12[(MoV2O4)4(O3PCH2PO3)4(SO3)2]39H2O (2b), and with mixed Na+ and NH4(+) counterions, Na+(NH4)11[(MoV2O4)4(O3PCH2PO3)4(SO3)2].13H2O (2d). With [O3PCH2PO3]4- extra ligands, the octanuclear wheel Li12(NH4)2[(MoV2O4)4(O3PCH2PO3)4(HO3PCH2PO3)2].31H2O (4a) was isolated with Li+ and NH4+ counterions and Li14[(MoV2O4)4(O3PCH2PO3)4(HO3PCH2PO3)2].34H2O (4c) as a pure Li+ salt. A new rectangular anion, formed by connecting two MoV dimers and two MoVI octahedra via methylenediphosphonato ligands with NH4+ as counterions, (NH4)10[(MoV2O4)2(MoVIO3)2(O3PCH2PO3)2(HO3PCH2PO3)2].15H2)O (3a), and Li9(NH4)2Cl[(MoV2O4)2(MoVIO3)2(O3PCH2PO3)2]. 22H2O (3d) as a mixed NH4+ and Li+ salt have also been synthesized. The structural characterization of the compounds, combined with a study of their behavior in solution, investigated by 31P NMR, has allowed a discussion on the influence of the counterions on the structure of the anions and their stability. Density functional theory calculations carried out on both isomers of the [(MoV2O4)4(O3PCH2PO3)4(SO3)2]12- anion (2), either assumed isolated or embedded in a continuum solvent model, suggest that the anti form is favored by approximately 2 kcal mol(-1). Explicit insertion of two solvated counterions in the molecular cavity reverses this energy difference and reduces it to less than 1 kcal mol(-1), therefore accounting for the observed structural versatility.     

Template synthesis of [(Mo(V)2O4)(O3PCH2PO3)]n clusters (n = 3, 4, 10): solid state and solution studies

The influence of three exogenous ligands (acetate, formate and carbonate) on the condensation process of the [Mo2O4]2+ dioxocation with the [O3PCH2PO3](4-) group has been investigated. Four cyclic or bicyclic compounds have been isolated and characterized by X-ray diffraction studies. Two closely related acetato and formato ovoidal duodecanuclear compounds, Na24[Na4(H2O)6[(Mo2O4)10(O3PCH2PO3)10(CH3COO)8(H2O)4]].103H2O (1) and Na28[Na2[(Mo2O4)10(O3PCH2PO3)10(HCOO)10]].110H2O (2), respectively, have been obtained. Their structures can be described as two interconnected nonequivalent wheels, delimiting a large cavity. When the condensation is performed in similar conditions but replacing carboxylato groups by carbonato ligands, the ellipsoidal octanuclear Na11[Na(H2O)2[(Mo2O4)4(O3PCH2PO3)4(CO3)2]].70H2O (3) compound is isolated. 31P NMR spectroscopic studies have shown that complexes 1 and 3 are stable in solution at room temperature. Nevertheless, on heating an aqueous solution of 3, the Na8[(Mo2O4)3(O3PCH2PO3)3(MoO4)].18H2O (4) complex, free of carbonato groups, is obtained. 4 is a hexanuclear Mo(V) wheel encapsulating a tetrahedral [Mo(VI)O4](2-) anion. Its rational synthesis using a controlled Mo(V)/Mo(VI) ratio is also presented.     

正烷基单胺对层状甘氨酸-N，N-双甲基膦酸锆的插层

The layered zirconium glycine-N,N-dimethylphosphonate (ZGDMP) was prepared and the intercalation behavior of n-alkylmonoamines was investigated. The X-ray diffraction powder patterns demonstrated that the n-alkylmonoamines were taken up in one step and there were no other intermediate phases. The interlayer distance correlated with the number of carbon atoms of the n-alkylmonoamine chains. The n-alkylmonoamines were intercalated into ZGDMP in such a way that the protons of the interlayer -CO₂H groups were replaced by the terminal -NH₃⁺ of the protonated n-alkylmonoamines. The intercalated n-alkylmonoamines were released from the lamellar ZGDMP at temperature of 150 to 250 ℃.     

The hydrothermal syntheses and characterization of one- and two-dimensional structures constructed from metal-organic derivatives of polyoxometalates: [(Cu(bpy)2)(Cu(bpy)(H2O))(Mo5O15)(O3P(CH2)4PO3)].H2O and [(u2(tpypyz)(H2O)2)(Mo5O15)(O3PCH2CH2PO3)].5.5H2O [bpy = 2,2'-bipyridine,tpypyz = tetra(2-pyridyl)pyrazine

The hydrothermal reaction of CuSO(4).5H2O, Na2MoO(4).2H2O and 2,2'-bipyridine with the bridging diphosphonate ligand H2O3P(CH2)4PO3H2 yields the one-dimensional chain [(Cu(bpy)2)(Cu(bpy)(H2O)2)(Mo5O15)(O3P(CH2)4PO3)].H2O; the introduction of a second bridging component in the reaction of Cu(MeCO2)2.H2O, MoO3, H2O3PCH2CH2PO3H2 and tetra(2-pyridyl)pyrazine yields the network solid [(Cu2(tpypyz)(H2O)2)(Mo5O15)(O3PCH2CH2PO3)].5.5H2O.     

Synthesis and characterization of the open-framework barium bisphosphonate [Ba3(O3PCH2NH2CH2PO3)2(H2O)4].3H2O

Following the strategy of using polyfunctional phosphonic acids for the synthesis of open-framework metal phosphonates, the phosphonocarboxylic acid (H2O3PCH2)2NCH2C6H4COOH was used in the hydrothermal synthesis of new Ba phosphonates. Its decomposition led to the first open-framework barium phosphonate [Ba3(O3PCH2NH2CH2PO3)2(H2O)4].3H2O. The synthesis was also successfully performed using iminobis(methylphosphonic acid), (H2O3PCH2)2NH, as a starting material, and the synthesis was optimized to obtain as a pure material. The reaction setup as well as the pH are the dominant parameters, and only a diffusion-controlled reaction led to the desired compound. The crystal structure was solved from single-crystal data: monoclinic; C2/c; a=2328.7(2), b=1359.95(7), and c=718.62(6) pm; beta=98.732(10) degrees ; V=2249.5(3)x10(6) pm3; Z=4; R1=0.036; and wR2=0.072 (all data). The structure of [Ba3(O3PCH2NH2CH2PO3)2(H2O)4].3H2O is built up from BaO8 and BaO10 polyhedra forming BaO chains and layers, respectively. These are connected to a three-dimensional metal-oxygen-metal framework with the iminobis(methylphosphonic acid) formally coating the inner walls of the pores. The one-dimensional pores (3.6x4 A) are filled with H2O molecules that can be thermally removed. Thermogravimetric investigations and temperature-dependent X-ray powder diffraction demonstrate the stability of the crystal structure up to 240 degrees C. The uptake of N,N-dimethylformamide and H2O by dehydrated samples is demonstrated. Furthermore, IR, Raman, and 31P magic-angle-spinning NMR data are also presented.     

(CH3)2NH(CH2)2NH(CH3)2][(UO2)2F2(HPO4)2]: a new organically templated layered uranium phosphate fluoride--synthesis, structure, characterization, and ion-exchange reactions

A new organically templated layered uranium phosphate fluoride, [(CH(3))(2)NH(CH(2))(2)NH(CH(3))(2)][(UO(2))(2)F(2)(HPO(4))(2)] has been synthesized by hydrothermal reaction of UO(3), H(3)PO(4), HF, and (CH(3))(2)NCH(2)CH(2)N(CH(3))(2) at 140 degrees C. [(CH(3))(2)NH(CH(2))(2)NH(CH(3))(2)][(UO(2))(2)F(2)(HPO(4))(2)] has a layered crystal structure consisting of seven-coordinated UO(5)F(2) pentagonal bipyramids and four-coordinated HPO(4) tetrahedra. Each anionic layer containing three-, four-, and six-membered rings is separated by [(CH(3))(2)NH(CH(2))(2)NH(CH(3))(2)](2+) cations. The [(CH(3))(2)NH(CH(2))(2)NH(CH(3))(2)](2+) cations may be readily exchanged with the M(2+) ions (M = Ba, Sr and Ca) in water to give high crystalline AE(UO(2))(2)(PO(4))(2).6H(2)O (AE = Ca, Sr, Ba).     

One- and two-dimensional silver and zinc uranyl phosphates containing bipyridyl ligands

The reaction of AgCN with UO2, 4,4'-bipy, and phosphoric acid in water at 160 degrees C under autogeneously generated pressure results in the formation of [Ag(4,4'-bipy)]2[(UO2)2H3(PO4)3] (AgUP-1). Ag(2,2'-bipy)(UO2)2(HPO4)(PO4) (AgUP-2) has been prepared from the hydrothermal reaction (at 180 degrees C) of KAg(CN)2 with UO2(C2H3O2)2.2H2O and 2,2'-bipy. [Zn(2,2'-bipy)]2[UO2(HPO4)3] (ZnUP-1) was isolated from the hydrothermal reaction of UO2, 2,2'-bipyridyl, Zn(CN)2, and H3PO4. Single crystal X-ray diffraction experiments reveal that the structure of AgUP-1 consists of 2infinity[(UO2)2H3(PO4)3]2- expanded autunite-like layers in the [ac] plane, separated by 1infinity[Ag(4,4'-bipy)]+ chains of two-coordinate Ag+ bridged by 4,4'-bipy. The structure of AgUP-2 is composed of chains of edge-sharing UO7 pentagonal bipyramids that are linked by phosphate anions into 2infinity[(UO2)2(HPO4)(PO4)]1- sheets with the beta-uranophane topology that extend in the [ab] plane. Both sides of the sheets are decorated by [Ag(2,2'-bipy)]+ units, where the Ag+ cations are found in distorted trigonal planar environments. The structure of ZnUP-1 is 1D and consists of UO7 pentagonal bipyramids that are connected by phosphate anions that also bind four-coordinate zinc(II) to the periphery of the chains and five-coordinate zinc within the chains. Intense fluorescence from these compounds was observed.