水、氯配位的Shiff碱单核及双核锰化合物的合成与结构表征

在水杨醛与二元胺形成的Schiff碱与Mn盐的反应体系中分离出两个单核Mn化合 物,(salen)Mn(H_2O)Cl(1)和[(salpr)Mn(H_2O)_2]Cl(2),并测定了结构。应用对 苯二甲酸在碱性条件下拉接两个单核Mn的Schiff碱配位单元,生成(salen)_2Mn_2 [μ-p-C_6H_4(COO)_2](H_2O)(CH_3OH)(3)并进行了结构表征。讨论了这些化合物 的红外及~1HNMR谱,揭示了Mn中心对配体信号的影响。     

一类环丙烷螺环化合物的简易合成和结构表征

以乙二醇二甲醚为溶剂,在K2CO3及痕量水存在下,鉮盐和多取代贫电子烯烃反应,高立体选择性合成了顺-1-甲氧羰基-2-取代芳基-6-环己烷基-5,7-二氧杂螺-〔2,3〕-4,8-二酮。采用IR、MS、1H NMR、13C NMR、DEPT及二维核磁共振技术对所合成的化合物进行了结构表征,并以NOESY实验确定了该化合物为顺式结构的环丙烷衍生物。     

水溶性有机膦盐的合成与表征

高产率地合成了三苯基磷间磺酸铵[MPA,(C6H5)2P(m-C6H4SO3^-NH4 )]和两种季膦盐[MPAE,(C6H5)2P^ (m-C6H4SO3^-)CH2CO2Et],[TPEI,(Ph3CH2CO2Et)I^-],初步研究了其理化性质。     

含硫过渡金属基元的反应 2: 双膦及双齿巯基混合配位钴, 镍化合物的合成和结构特征

双膦(P-P)和1, 2-双齿巯基(S-X)混合与MCl2(M=Co, Ni)反应,得到通式为M(S-X)(P-P)的产物。晶体结构测定表明, 配合物Co(bdt)(dppe)(1), Ni(tdt)(dppm)(2)和Ni(tsal)(dppe)(3)中的金属均为SXP2配位的四方平面构型, S, X, P原子分别来自二种双齿配体, 各形成四、五或六元螯合配位环。文中总结了结构特征, 探讨了基元配合物稳定的原因。     

含硫过渡金属基元的反应 2: 双膦及双齿巯基混合配位钴, 镍化合物的合成和结构特征

双膦(P-P)和1, 2-双齿巯基(S-X)混合与MCl2(M=Co, Ni)反应,得到通式为M(S-X)(P-P)的产物。晶体结构测定表明, 配合物Co(bdt)(dppe)(1), Ni(tdt)(dppm)(2)和Ni(tsal)(dppe)(3)中的金属均为SXP2配位的四方平面构型, S, X, P原子分别来自二种双齿配体, 各形成四、五或六元螯合配位环。文中总结了结构特征, 探讨了基元配合物稳定的原因。     

膦桥多核银络合物[Ag_4(dppe)_3(NO_3)_4]的合成与结构

膦桥过渡金属络合物和簇合物由于独特的结构特性和催化性能而引起人们的重视,许多这类的化合物已被合成和表征,但相应的银化合物的研究则较少。近年来,我们利用双齿膦配体dppm(Pb_2pCH_2PPh_2)和dppe(Ph_2PCH_2CH_2PPh_2)合成了一系列新型的膦配体银络合物。这些双齿膦配体结合硝酸根、氯离子和吡啶等配体以多种方式与银原子配位,呈现了丰富的配位结构特征。本文报导另一个新的dppe多核银络合物的合成与晶体结构测定的结果,讨论了其特殊的结构特征。     

膦桥多核银络合物[Ag4(dppe)3(NO3)4]的合成与结构

A new polynuclear silver complex with bridging diphorsphine ligand has been synthesized and characterized by :single cryatsl X-ray diffraction method The compound crystallizes in the triclinic space group P1 with a=1.27489, b=1.34715, c=1.47015 nm; α=59.747, β=63.949, γ=70.196°; V=1.9369 nm. The simplest formularis [Ag_4· dppe)_3(NO_3)_4], Mr=1874.79, D_c=1.607 g·cm~(-3), Dm=1.62 g·cm~(-3), μ(MoKa)=11.69 cm~(-1), F(OOO)=942. The structure was solved by conventional heavy-atom techniques and refined by full-matrix least squares to give discrepany indices of R=0.048 and RW=0.060(W=1/[σ(Fo)~2+(PWT*Fo)~2+QWT]-Fo) for 5052 reflections. An empirical absorption correction program DIFABS was performed.Silver atoms are linked by bridging ligands of dppe and nitrate, forming a network extending in space. Each structural unit contains two binuclear subunits, of which silver atoms are bridged by nitrates. The two subunits are connected by one dppe ligand. Silver atoms are not equivalent in subunit and one of the nitrates functions not only as a monodentate bridging ligand, but also as an asymmetric bidentate chelating lingand. All coordinate configurations of silver are shown as distorted tetrahedron.     

二正丁基锡(Ⅳ)-邻菲咯啉-单核苷酸混配配合物的合成与表征

本文研究了二正丁基邻菲咯啉二氯锡(Ⅳ)(n-Bu)2SnCl2(phen)与单核苷酸(Nu)在近生理pH水溶液中的作用, 结果表明, 二正丁基邻菲咯啉二氯锡(Ⅳ)的一个顺氯原子被单核苷酸取代, 得到了(n-Bu)2Sn(phen)(Nu)Cl型混配新配合物,单核苷酸以磷酸根氧原子与锡(Ⅳ)键合, 并给出了其结构。     

新型单膦配位羧酸银配合物的合成、表征及其热稳定性的研究(英)

0 IntroductionIn recent years, silver carboxylates have attractedmany interests, mostly because they are promisingcandidates in the growth of metal thin films via metal-organic chemical vapor deposition (MOCVD) tech-niques. These sliver compounds show low light sensi-tivity and relatively high thermal stability. Several ex-amples of bisphosphine ligands coordinated silver car-boxlylates have been reported[1￣4].Monophosphine coordinated silver complexes areexpected to have better volatility,…     

Synthesis and Crystal Structure of a New 2D Honeycomb-like Cadmium(II) Complex with Tripodal Ligand

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系列过渡金属与三角架多咪唑配合物的合成、结构及表征

以三氨乙基胺和N－甲基咪唑醛为原料合成了三角架多咪唑配体((min)₃tren)，并合成了五个过渡金属配合物：[Zn(min)₃tren](ClO₄)₂1， [Cu(min)₃tren](ClO₄)₂2, [Ni(min)₃tren](ClO₄)₂3, [Co(min)₃tren](ClO₄)₂4, and [Mn(min)₃tren](ClO₄)₂CH₃CN 5，通过元素分析，摩尔电导率，红外和电子光谱确定了化合物的组成。对配合物4和5进行了晶体结构测定。结果表明，在这两个化合物中金属原子均处于扭曲的八面体配位环境，分别与三个亚胺氮原子和三个咪唑氮原子配位。配合物4和5的电化学研究表明在乙腈溶液中，有[Co-O₂]^n-和[Mn-O₂]^n-存在，认为4和5是很好的超氧化物清除剂。     

A Pyridine-copper Inclusion Complex of a New Tripodal Ligand

1 INTRODUCTION Numerous recent reports have been focused on the construction of supramolecular architectures by using some special tripodal ligands with aromatic ring platforms[1～5]. Mixing this kind of ligands with metal ions in a suitable solution generally yields typical 1D, 2D and 3D coordination polymers or large nanometer-sized cavities supposed to be use- ful for catalysis, molecular selection, ion exchange, specific chemical transformations et al.[6～11]. Now our group is inte…     

Synthesis and Crystal Structure of a New Mn8 Compound with Tripodal Ligand

A new manganese compound [Mn8(tmp)2(Htmp)4((CH3)3CCO2)4(py)2Cl2]·2py (1·2py, H3tmp = 1,1,1-tri(hydroxymethyl)propane, py = pyramid) has been synthesized and its structure was characterized by IR, elemental analysis and X-ray diffraction. Compound 1 belongs to the triclinic system, space group P1 with a = 13.378(5), b = 14.334(5), c = 15.012(6) , α = 107.637(5), β = 95.635(3), γ = 92.825(4)°, V = 2720.7(17) 3, Z = 1, C76H124N4O26Cl2Mn8, Mr = 2022.23, Dc = 1.234 Mg/m3, μ = 1.007 mm-1, F(000) = 1052, T = 293(2) K, the final R = 0.0755 and wR = 0.2163 for all 6463 observed reflections (I > 2σ(I)). X-ray analysis shows that the core of 1 contains a [Mn8] mixed-valence rod-like unit consisting of six edge-sharing triangles (Mn3), each of which is bridged by a μ3-oxygen atom.     

酰胺型三足配体硝酸铽超分子配合物的晶体结构与荧光性质

通过硝酸铽与新型酰胺型三足配体L (2,2',2'-胺三乙酰苯胺)之间的反应得到配合物[TbL₂(H₂O)]• (NO₃)₃(H₂O)₂(CH₃OH), 并用X射线单晶衍射测定了配合物的晶体结构. 配合物为酰胺型三足配体稀土硝酸盐配合物中首例1∶2 (M∶L)型配合物. 配合物为单斜晶系, P21/c空间群, 晶胞参数a＝1.2870(7) nm, b＝1.6590(8) nm, c＝2.8723(12) nm, β＝115.364(2)°, V＝5.5415(5) nm³, Z＝4, R＝0.0399, wR＝0.0922, Tb^3＋为9 配位, 呈变形的三帽三角棱柱配位构型. 配合物分子单元通过分子间氢键作用将整个分子连接成三维网状超分子结构. 室温下, 在紫外光激发下配合物固体表现出Tb^3＋的特征荧光发射.     

Synthesis and Crystal Structure of a New 2D Honeycomb—like Cadmium （Ⅱ） Complex with Tripodal Ligand

A new cadmium (II) coordination polymer, [Cd(TTTMB)₂]‐(SO₄) · 21H₂O, where TTTMB =1,3, 5‐tris (imidazol‐1‐yl‐methyl)‐2,4,6‐trimethylbenzene, was obtained by self‐assembly of tripodal ligand TTTMB with CdSO₄·2.7H₂O in acetonitrile, and characterized by X‐ray crystallography. The crystal data belongs to monoclinic space group C_c with cell parameters a = 1.16891(4) nm, b=2.06671(6) nm, c = 2.48185(7) nm, β = 97.8560(10)°, R = 0.0487, wR = 0.1211. The results of structure analysis indicate that each TTTMB ligand coordinates three metal atoms and in turn each Cd(II) atom with octahedral coordination geometry connects six nitrogen atoms of imidazole group from six different TTTMB ligands to produce a 2D honeycomb network structure. There are a lot of water molecules linked by hydrogen bonds and occupied the channels formed intra‐ and inter‐sheets.     

1，3，5－三咪唑基苯－醋酸锌配合物的合成、结构和离子交换性质研究

报道了一个由新型三角架配体1,3,5-三咪唑基苯（L）与Zn(CH_3COO)_2· 2h_2O组装得到的配合物：[Zn(L)_2(H_2O)_2]-(CH_3COO)_2·2H_2O (1)，用X射线 单晶衍射法测定了配合物的晶体结构，该晶体属单斜晶系，空间群P2_1/n，晶胞参 数a = 0.8339(1) nm, b = 1.2209(2) nm, c = 1.7565(3) nm, β = 94.880(3)° ，D_c = 1.383 g/cm~3, μ = 1.505 mm~(-1), F(000) = 1560, R_1 = 0.0429, wR_2 = 0.0713。配合物1具有二维层状结构，醋酸根阴离子位于层与层之间的孔 道中，并且可以被硝酸根离子交换。     

Thermodynamic Stability Research of Metal Complexes with a Tripodal Amide Ligand and Crystal Structure of its Cobalt（Ⅲ） Complex

A new Co（Ⅲ） complex with a tripodal amide ligand [CoL（N3）3] （L = N-acetyl- N＇,N＇-bis-[（2-pyridyl）methyl]-ethylenediamine） has been synthesized and characterized structurally by X-ray diffraction. It crystallizes in orthorhombic, space group Pnma with a = 9.2515（19）, b = 12.729（3）, c = 17.273（4） A, V = 2034.0（7） A3, C16H20CoN13O, Mr = 469.38, Dc = 1.533 g/cm3, μ（MoKα） = 0.884 mm^-1, F（000） = 968, Z = 4, the final R = 0.0392 and wR = 0.0818 for 2430 observed reflections. In the complex, the amide ligand L acts as a tridentate fashion and coordinates to the Co（Ⅲ） ion through three nitrogen atoms, while the other three positions of the Co（Ⅲ） center are occupied by three terminal azide anions. The complex is connected as a 1D chain structure by intermolecular hydrogen bonds between the uncoordinated amide groups. In order to investigate the coordination ability, thermodynamic stability of the ligand L with the first-series transition metal ions （Co（Ⅱ）, Ni（Ⅱ）, Cu（Ⅱ） and Zn（Ⅱ）） has been studied by potentiometric titration, and the results show that the order of their stability constants conforms to the Irving-Williams sequence.     

酰胺型三足体铜配合物[CuL][CuCl2(NO3)2]的合成及晶体结构

The title complex， [CuL][CuCl₂(NO₃)₂] [L=N，N，N′，N′，N″，N″-Hexaisopropyl-2， 2′， 2″-Nitrilotris(2，1-ethoxy)triacetamide]， has been synthesized by using an amide-type tripodal ligand with Cu(NO₃)₂ and then characterized by X-ray single crystal structure analysis. It belongs to monoclinic，space group P2₁/c with a=1.522 7(2) nm，b=1.277 8(2) nm， c=2.184 5(4) nm， β=93.680(10)°， V=4.241 6(12) nm³， Z=4， D_c=1.401 Mg·m^-3， μ=1.189 mm^-1， F(000)=1 880， and final R₁=0.050 9， wR₂=0.125 3. The results show a Cu(Ⅱ) ion was encapsulated by the three chains of the cup-like heptadentate ligand and four-coordinated by the central nitrogen atom and three oxygen atoms from the ligand. CCDC: 648900.     

Synthesis and Crystal Structure of a Novel Tetranuclear Manganese(II) Complex with a Tripodal Peptide Ligand

1 INTRODUCTION Amides play an important role in the evolution ofnature. The amidate participates in the coordinationof iron with the ligands containing biomolecules, suchas antitumor drug bleomycin[1] and nitrile hydra-tase[2]. Bleomycin is a clinically useful antitumoragent which catalyzes the cleavage of oxidative DNAand oxidizes a number of organic substrates with di-oxygen or H2O2 . This has raised more interest in [3]the coordination of amide complexes[4, . …