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1.
A new assembly [Cu2(sac)2(μ‐dmea)2(μ‐H2O)]n (sac = saccharinate and Hdmea = 2‐dimethylaminoethanol) has been synthesized and characterized by elemental analysis, IR spectroscopy, thermal analysis and single crystal X‐ray diffraction. The complex crystallizes in the monoclinic space group C2/c and consists of dinuclear modules of [Cu2(sac)2(dmea)2]. The sac ligand is N‐coordinated, while the dmea ligand is in the deprotanated form by losing the ethanol hydrogen atom and acts as a bidentate donor through the alkoxo group and N atom. The alkoxo group also serves as a bridge between two copper(II) ions, leading to an intra‐dimer Cu···Cu separation of 3.0229(7) Å. The dimeric units are bridged by aqua ligands to generate a one‐dimensional water‐bridged helical chain, in which the copper(II) ions exhibit a distorted square‐pyramidal CuN2O3 coordination. The Cu–Cu distance in the chain separated by the bridging aqua ligands is 5.297Å. The polymeric chains are further linked by π(sac)···π(sac) and C–H···π(sac) interactions into a two‐dimensional supramolecular network. 相似文献
2.
Trinuclear Cobalt(II) and Zinc(II) Salamo‐type Complexes: Syntheses,Crystal Structures,and Fluorescent Properties
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Wen‐Kui Dong Fan Zhang Na Li Li Xu Yang Zhang Jing Zhang Li‐Chun Zhu 《无机化学与普通化学杂志》2016,642(7):532-538
Two trinuclear CoII and ZnII complexes, [(CoL)2(OAc)2Co] and [(ZnL)2(OAc)2Zn], with an asymmetric Salen‐type bisoxime ligand [H2L = 4‐(N,N‐diethylamine)‐2,2′‐[ethylenediyldioxybis(nitrilomethylidyne)]diphenol] were synthesized and characterized by elemental analyses, IR, UV/Vis, and fluorescent spectroscopy. The crystal structures of the CoII and ZnII complexes were determined by single‐crystal X‐ray diffraction methods. The CoII atom is pentacoodinated by N2O2 donor atoms from the (L)2– unit and one oxygen atom from the coordinated acetate ion, resulting in a trigonal bipyramid arrangement. With the help of intermolecular hydrogen bonding C–H ··· O and C–H ··· π interactions, a self‐assembled continual zigzag chain‐like supramolecular structure is formed. The ZnII atom is pentacoodinated by N2O2 donor atoms from the (L)2– unit and one oxygen atom from the coordinated acetate ion, resulting in an almost regular trigonal bipyramid arrangement. A self‐assembled continual 1D supramolecular chain‐like structure is formed by intermolecular hydrogen bonding C–H ··· O and C–H ··· π interactions. Additionally, the photophysical properties of the CoII and ZnII complexes were discussed. 相似文献
3.
Quan‐Yan Wen Jian‐Qiao Chen Hua‐Cai Fang Li Chen Zheng‐Yuan Zhou Zuo‐Jun Hu Yue‐Peng Cai Prof. Dr. 《无机化学与普通化学杂志》2009,635(3):567-571
A ZnII compound based on the semi‐rigid dipolar ligand 1,4‐bis(benzimidazol‐1‐ylmethyl)benzene (L), {[Zn( L )2Cl2]·2DMF}n ( 1 ) has been synthesized successfully under solvothermal conditions. X‐ray single crystal diffraction shows that the complex contains P‐helical and M‐helical chains with 21 screw axis but crystallizes as a racemate. Through π···π stacking interactions between two well‐overlapping benzimidazoleyl rings from two adjacent chains, the 3D racemic supramolecular network is assembled. Furthermore, the IR, TGA and luminescent properties are also investigated in this work. 相似文献
4.
A complex with eight‐coordinate lead(II ) atom and saccharinate (sac) and 2‐aminomethylpyridine ligands was characterized by IR, elemental analysis and X‐ray crystallography. The lead(II ) complex crystallizes in the monoclinic crystal system with space group P21/c. The single crystal X‐ray analysis shows that the complex is a coordination polymer, [Pb(ampy)(μ‐sac)2]n, in which the lead(II ) ions have a highly distorted bicapped trigonal antiprism coordination. Lead(II ) ions are bridged by carboxyl groups of sac forming one‐dimensional linear chains, running parallel to the a axis. The intrachain Pb···Pb distances are 4.4490(3) and 4.4679(3)Å. The individual chains are connected by N—H···Osulfonyl and Campy—H···Osulfonyl type hydrogen bonds, resulting in a three‐dimensional network. The sac ligand acts as bidentate and bridging ligand, while ampy behaves as an N, N′ donor. The IR spectra of the lead(II ) complex are discussed in detail. 相似文献
5.
Synthesis,Spectral, Thermal Studies of Co(II), Ni(II), Cu(II) and Zn(II)‐arginato Complexes. Crystal Structure of Monoaquabis(arginato‐κO,κN)copper(II). [Cu(arg)2(H2O)].NaNO3
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Dursun Ali Köse Emre Toprak Emre Avcı Gülçin Alp Avcı Onur Şahin Orhan Büyükgüngör 《中国化学会会志》2014,61(8):881-890
Transition metal complexes of arginine (using Co(II), Ni(II), Cu(II) and Zn(II) cations separately) were synthesized and characterized by FTIR, TG/DTA‐DrTG, UV‐Vis spectroscopy and elemental analysis methods. Cu(II)‐Arg complex crystals was found suitable for x‐ray diffraction studies. It was contained, one mole CuII and Na+ ions, two arginate ligands, one coordinated aqua ligand and one solvent NO3? group in the asymmetric unit. The principle coordination sites of metal atom have been occupied by two N atoms of arginate ligands, two carboxylate O atoms, while the apical site was occupied by one O atom for CuII cation and two O atoms for CoII, NiII, ZnII atoms of aqua ligands. Although CuII ion adopts a square pyramidal geometry of the structure. CoII, NiII, ZnII cations have octahedral due to coordination number of these metals. Neighbouring chains were linked together to form a three‐dimensional network via hydrogen‐bonding between coordinated water molecule, amino atoms and O atoms of the bridging carboxylate groups. CuII complex was crystallized in the monoclinic space group P21, a = 8.4407(5) Å, b = 12.0976(5) Å, c = 10.2448(6) Å, V = 1041.03(10) Å3, Z = 2. Structures of the other metal complexes were similar to CuII complex, because of their spectroscopic studies have in agreement with each other. Copper complex has shown DNA like helix chain structure. Lastly, anti‐bacterial, anti‐microbial and anti‐fungal biological activities of complexes were investigated. 相似文献
6.
Two new iron(III) complexes and one iron(II) complex have been synthesized from the solvothermal reactions of FeCl3·6H2O with 3,5‐bis(pyridin‐2‐yl)‐1,2,4‐triazole (Hbpt) in methanol or acetonitrile. KSCN acted as the reducing agent in the synthesis of iron(II) complex of 3 . [FeCl3(Hbpt)(H2O)]·H2O ( 1 ) crystallizes in the triclinic space group with a = 7.475(1), b = 9.468(2), c = 12.309(2) Å, α = 73.880(2), β = 74.746(2), γ = 81.849(2)°, V = 805.2(2) Å3, Z = 2. [Fe2(bpt)2Cl4] ( 2 ): orthorhombic space group Pnnm with a = 9.895(2), b = 10.632(2), c = 13.195(2) Å, V = 1388.1(4) Å3, Z = 2. [Fe2(bpt)2(MeOH)2Cl2] ( 3 ): orthorhombic space group Pbca with a = 14.4204(16), b = 9.8737(11), c = 19.792(2) Å, V = 2818.1(5) Å3, Z = 4. 1 features the first structurally characterized metal complex of the neutral Hbpt ligand in which the Hbpt ligand adopts an unprecedented zwitterionic form. 2 shows a neutral dinuclear iron(III) complex and the [Fe2(bpt)2]4+ unit is ideally planar. The two iron(III) ions separated by a distance of 4.408(2) Å are doubly triazolate‐bridged. Each dimeric unit is connected with six other dimeric ones via the bifurcated C‐H···Cl hydrogen bonds, these connections extend the dimeric moieties into a three‐dimensional molecular architecture. 3 is a neutral centrosymmetric dinuclear FeII complex, in which intermolecular moderate O‐H···N hydrogen bonding interactions between the methanol molecules and 4‐position nitrogen atoms of the triazolato groups extend the dinuclear species into a two‐dimensional supramolecular architecture of (4,4) topology. Magnetic studies indicate there exists an antiferromagnetic spin coupling in FeIII2 and FeII2 units via the double triazolate bridges in 2 and 3 . 相似文献
7.
A new calcium(II) complex of the saccharinate ligand (sac) with 2—hydroxyethylpyridinium (Hpyet) was synthesized and characterized by elemental analysis, FT—IR spectroscopy, thermal analysis and single crystal X—ray diffractometry. The [Ca(sac)2(H2O)2(Hpyet)2](sac)2 complex crystallizes in the triclinic space group (P1¯) with the cell dimensions a = 7.4360(7)Å, b = 12.5263(12)Å, c = 12.8329(13)Å, α = 82.534(8)°, β = 75.202(8)° and γ = 89.662(8)° (293 K). The title complex consists of a complex cation and two sac anions. In the complex cation, the calcium(II) ion is six—coordinate, bonding to two aqua ligands, two Hpyet ligands andtwo sac ligands located in the trans positions. Two of the sac ions are coordinated to the calcium(II) ion through the carbonyl O atom, while the other two remain outside the coordination sphere as the counter—ions. Thermal decomposition of the complex in air results in elimination of aqua, Hpyet, and sac ions, respectively. 相似文献
8.
The self‐assembly of 1, 0‐phenanthroline (phen) and 1,2,4,5‐benzenetetracarboxylic acid(H4btc) with Ca(NO3)2 gives rise to a two‐dimensional network structure coordination polymer, [Ca(phen)(btc)0.5(H2O)] ( 1 ), which was characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction. This compound is monoclinic, space group C2/c, with Z = 8 in a unit cell with dimensions a = 21.744(3) Å, b = 10.0151(12) Å, c = 14.7122(17) Å, β = 110.2850(10)°. The structure contains one crystallographic unique CaII atom, one phen coordinated molecule and a half of btc4– anion. The phen molecule acts as a didentate ligand chelating with a CaII atom, whereas the btc4– anion acts as a μ6‐bridge linking six different CaII atoms to form a two‐dimensional network with (4, 4) topological structure. The three dimensional stacking structures are formed by C–H ··· O hydrogen bonding and π–π interaction. The thermal stability and fluorescent properties of 1 were investigated. Calcite particles are produced by calcination of compound 1 at 580 °C. The obtained calcite was characterized by XRD and SEM analyses. 相似文献
9.
A one‐dimensional copper(II) complex {[Cu(sac)2(μ‐pyz)(H2O)]·H2O}n ( 1 ) (pyz = pyrazine, and sac = saccharinate) has been synthesized and characterized by elemental analysis, IR spectroscopy, thermal and single crystal X‐ray analyses. Complex 1 crystallizes in the triclinic space group . The [Cu(sac)2(H2O)] units are bridged by pyz leading to a one‐dimensional alternating chain in which the copper(II) ions exhibit a distorted square–pyramidal coordination of CuN4O. The intradimer Cu···Cu distance is 6.881Å, while interdimer Cu···Cu distance is 7.066Å. The supramolecular interactions are mainly controlled by the sac anion and water molecules. The individual chains are linked by strong OW–H···O(sac) hydrogen bonds into a two‐dimensional layers, which are further arranged in a three‐dimensional supramolecular network by aromatic π(sac)···π(sac) stacking interactions and CH···π(pyz) interactions. Thermal analysis of complex 1 shows that the decompositions of the aqua, pyz and sac ligands are observed as distinct steps on the DTA and TG curves. 相似文献
10.
Jing‐Yuan Xu He‐Dong Bian Qing‐Lun Wang Wen Gu Shi‐Ping Yan Dai‐Zheng Liao Peng Cheng Zong‐Hui Jiang Pan‐Wen Shen 《无机化学与普通化学杂志》2003,629(6):1063-1067
Two new transition metal(II) complexes [M(hdpa)2(N(CN)2)2] (M = Mn ( 1 ), Co ( 2 ); hdpa = 2, 2'‐dipyridylamine) have been prepared and characterized structurally and magnetically. Both compounds crystallize in the monoclinic space group C2/c. 1 and 2 are isotypic with the unit cell parameters a = 8.634(9), b = 13.541(14), c = 21.99(2) Å, β = 94.806(18)°, and V = 2562(5) Å3 for 1 , a = 8.617(3) Å, b = 13.629(5)Å, c = 21.598(8)Å, β = 94.593(6)°, and V = 2528.4(15)Å3 for 2 , and Z = 4 for both. According to X‐ray crystallographic studies, each metal(II) ion was six‐coordinated with four nitrogen atoms from two bidentate hdpa ligand and two nitrogen atoms from two N(CN)— anions to form slightly distorted octahedrons. Adjacent complex molecules are connected by hydrogen bonds or π···π interactions to form three‐dimensional network. The IR and UV spectroscopy were measured and the magnetic behaviors were investigated. 相似文献
11.
Shabnam Sheshmani Parvaneh Dalir Kheirollahi Hossein Aghabozorg Ardeshir Shokrollahi Guido Kickelbick Mojtaba Shamsipur Farshid Ramezanipour Abolghasem Moghimi 《无机化学与普通化学杂志》2005,631(15):3058-3065
The two complexes (pydaH)2[Ce(pydc)2(H2O)2]2 · 2H2O (1) and (phenH)2[Bi(pydc)2(H2O)]2 · 5H2O (2) were prepared from the proton transfer compounds containing the 2,6‐pyridinedicarboxylate ion. 1 was synthesized from the reaction of Ce(NO)3 · 6H2O with the proton transfer compound, (pydaH2)(pydc), (pyda=2,6‐diaminopyridine, pydcH2=2,6‐pyridinedicarboxylic acid). 2 was synthesized from the reaction of proton transfer compound, (phenH)2(pydc), (phen=1,10‐phenanthroline), with Bi(NO3)3 · 5H2O. The characterization was carried out using IR, 1H and 13C NMR spectroscopy, elemental analysis and single crystal X‐ray diffraction. The complex 1 crystallizes in the space group of the triclinic system, and contains two molecules per unit cell. The structure has been refined to a final value for the crystallographic R factor of 0.0342 based on 8851 reflections. The unit cell parameters are: a = 9.753(2) Å, b = 10.503(2) Å, c = 10.774(2) Å, α = 83.905(4)°, β = 88.089(4)°, and γ = 82.636(3)°. The crystal structure illustrates that cerium atoms are connected together through the four‐membered ring Ce2O2. 2,6‐Pyridinedicarboxylate fragment acts as a tridentate ligand. The molecular structure contains four (pydc)2? ligands, two of which are bridge ligands linking the two central atoms. The complex 2 crystallizes in the space group of the triclinic system and contains two molecules per unit cell. The unit cell dimensions are: a = 8.8860(4) Å, b = 12.0132(6) Å, c = 13.0766(6) Å, α = 100.967(1)°, β = 96.681(1)° and γ = 94.191(1)°. The structure has been refined to a final value for the crystallographic R factor of 0.0471 based on 9576 reflections. In this complex, 2,6‐pyridinedicarboxylate moiety has acted as a tridentate ligand and the lattice is composed of binuclear unit, [Bi(pydc)2(H2O)]22?, (phenH)+ counter ions and five lattice waters. In both complexes hydrogen bonds, π‐π stacking and ion‐pairing play important roles in stabilizing the corresponding lattice. The stoichiometry and stability of the ZnII, CdII, PbII, and CeIII complexes with (pydaH2)(pydc) in aqueous solution were investigated by potentiometric pH titration. The solution studies revealed that the stoichiometry of the crystalline complexes of the proton transfer system (pydaH2)(pydc) with CeIII, obtained in this study, and those with ZnII, CdII and PbII, reported in our previous studies, are in close agreements. The complexation reactions of phen, pydc, and 2phen+pydc with BiIII in aqueous solution were investigated by potentiometric pH titrations, and the equilibrium constants for all major complexes formed are described. 相似文献
12.
Elena Bugella‐Altamirano Josefa María Gonzlez‐Prez Duane Choquesillo‐Lazarte Juan Nicls‐Gutirrez Alfonso Castieiras‐Campos 《无机化学与普通化学杂志》2000,626(4):930-936
The stoichiometric reaction of copper(II) hydroxycarbonate, iminodiacetic acid (H2IDA = HN(CH2CO2H)2) and α‐picolinamide (pya) in water yields crystalline samples of (α‐picolinamide)(iminodiacetato)copper(II) dihydrate, [Cu(IDA)(pya)] · 2 H2O ( 1 ). The compound was characterised by thermal (TG analysis with FT‐IR study of the evolved gasses), spectral (IR, electronic and ESR spectra), magnetic and single crystal X‐ray diffraction methods. It crystallises in the triclinic system, space group P1, a = 8.8737(4), b = 10.23203(5), c = 15.7167(11) Å, α = 77.61(1)°, β = 103.89(1)°, γ = 80.32(1)°, Z = 4, final R1 = 0.056. The asymmetric unit contains two crystallographic independent molecules but chemically very similar ones. The CuII atom exhibits a square base pyramidal coordination (type 4 + 1). pya acts as N,O‐bidentate ligand supplying two among the four closest donor atoms of the metal [averaged bond distances (Å): Cu–N = 1.982(2), Cu–O(amide) = 1.972(2)]. IDA plays a N,O,O′‐terdentate chelating role [averaged bond distances (Å): Cu–N = 2.004(3), Cu–O = 1.941(2) and Cu–O = 2.242(2)]. The coordinating behaviour of pya in 1 is discussed on the basis of its N,O‐bidentate chelating role and the preference of the ‘Cu‐iminodiacetato' moiety [Cu(IDA)] to link the N‐heterocyclic donor of pya in trans versus the Cu–N(IDA) bond. Consistently the ligand pya is able to impose a fac‐chelating configuration to IDA one around the copper(II) as previously has been reported to mixed‐ligand complexes having a 1/1/2 CuII/IDA/N(heterocyclic) donor ratio or a closely related 1/1/1/1 CuII/IDA/N(heterocyclic)/N(aliphatic) one. 相似文献
13.
Mohammad Reza Yaftian Saeed Rayati Reyhaneh Safarbali Niloofar Torabi Hamid Reza Khavasi 《Transition Metal Chemistry》2007,32(3):374-378
A new tetradentate N2O2-type Schiff base, bis(2-hydroxypropiophenone)-1,2-propanediimine (L), was synthesized by the reaction of 1,2-propanediamine with 2-hydroxypropiophenone in EtOH. The Schiff base is able to extract CoII, NiII, CuII and ZnII ions in aqueous NaNO3 media into a CH2Cl2 organic phase via a cation exchange mechanism. The observed extraction order was as follows: CuII > NiII > CoII > ZnII. Reaction of nickel acetate with the Schiff base in EtOH afforded the neutral complex Ni · L. Single crystals of this complex were obtained from mixed CHCl3-EtOH (3:1) solvent and its structure was determined by X-ray diffraction. Crystal data for Ni · L · CHCl3: triclinic, space group Pī, with a = 9.005(2) Å, b = 9.625(2) Å, c = 14.212(4) Å, V = 1136.8(5) Å3, α = 106.06(2)°, β = 106.06(2), γ = 105.10(2)°, and Z = 2. A near square planar structure is observed for the studied complex. 相似文献
14.
Xiuli Wang Prof. Hailiang Hu Baokuan Chen Hongyan Lin Guocheng Liu Jin Li 《无机化学与普通化学杂志》2009,635(15):2692-2696
Two new inorganic–organic vanadate hybrid compounds [Mn(Hbbi)2(V4O12)] ( 1 ) and [Cd(Hbbi)2(V4O12)] ( 2 ) (bbi = 1,1’‐(1,4‐butanediyl)bis(imidazole)) were hydrothermally synthesized and characterized by elemental analyses, IR spectroscopy, TG and single‐crystal X‐ray diffraction. The two compounds crystallize in monoclinic system, P21/c space group with a = 8.556(5) Å, b = 10.761(5) Å, c = 16.917(5) Å, β = 93.032(5) o, V = 1555.4(12) Å3, Z = 2, R = 0.0390 for 1 and a = 8.657(5) Å, b = 10.743 (5) Å, c = 16.864 (5) Å, β = 93.81(5)o, V = 1564.9 (12) Å3, Z = 2, R = 0.0717 for 2 . Single‐crystal X‐ray diffraction analysis reveals that the two compounds are isostructural and both consist of one‐dimensional (1D) chains, which are constructed from vanadate anion clusters and [M(Hbbi)2]4+ cation groups [M = MnII ( 1 ), CdII ( 2 )]. Moreover, the polymeric chains are ultimately packed into a three‐dimensional (3D) supramolecular framework through C–H ··· O and N–H ··· O hydrogen bonding interactions. 相似文献
15.
Abolghasem Moghimi Robabeh Alizadeh M. Carla Aragoni Vito Lippolis Hossein Aghabozorg Parviz Norouzi Francesco Isaia Shabnam Sheshmani 《无机化学与普通化学杂志》2005,631(10):1941-1946
The novel 1,10‐phenanthroline‐2,9‐dicarboxylate containing Chromium(III) complex, (pydaH)[Cr(phendc)2] · 5H2O, was synthesized using proton‐transfer compound LH2, (pydaH2)2+(phendc)2?, (pyda: 2,6‐pyridinediamine; phendcH2: 1,10‐phenanthroline‐2,9‐dicarboxylic acid) and thoroughly characterized by elemental analysis, IR spectroscopy, X‐ray crystallography and cyclic voltammetry. The complex crystallizes in the monoclinic space group P21/n with four formula units in the unit cell. The unit cell dimensions are: a = 13.962(3) Å, b = 14.529(3) Å, c = 16.381(3) Å and β = 106.691(4)°. In this complex, 1,10‐phenanthroline‐2,9‐dicarboxylate acts as a tridentate ligand and the lattice is composed of anionic hexacoordinated complex, [Cr(phendc)2]?, 2,6‐pyridiniumdiamine counter ion, (pydaH)+, and five lattice water molecules. Crystallographic characterization revealed that the resulting supramolecular structure is strongly stabilized by complicated network of hydrogen bonds between the crystallization water molecules, counter ion and both coordinated and uncoordinated carboxylate groups. There is no relevant π‐π interaction for this anionic complex between pyda or phendc moieties. The electrochemical studies indicated over potential for both the cathodic and anodic peaks of the complex with respect to the free Cr3+ ion, as a consequence of the energy requirement for rearrangement of the ligand at electrode surface. 相似文献
16.
Ning Pan Rui‐Zheng Wei Yan‐Hui Chi Jing‐Min Shi Wei Wei Yi‐Quan Zhang 《无机化学与普通化学杂志》2013,639(6):1026-1031
The mononuclear complex [Ni(HOphen)(OSO3)(H2O)3] · 5H2O (HOphen = 1, 10‐phenanthrolin‐2‐ol) was prepared and its single structure was determined by X‐ray crystallography. In this complex, the NiII ion has a distorted octahedral arrangement. Crystal structure analysis shows that two kinds of π–π stacking interactions and C–H ··· O short contact intermolecular interactions exist among the adjacent complexes. Fitting to the variable‐temperature magnetic susceptibility data gave the magnetic coupling constant, 2J = –0.98 cm–1. Theoretical calculations, based on density functional theory (DFT) coupling with the broken‐symmetry approach (BS), revealed that the π–π stacking magnetic coupling pathways resulted in weak ferromagnetic interactions with 2J = 4.86 cm–1 and 2J = 4.16 cm–1, respectively, for the adjacent NiII ions with separations of 8.568(19) Å and 8.749(32) Å, respectively; whereas the magnetic coupling pathway of the C–H ··· O short contact intermolecular interaction led to a weak antiferromagnetic interaction with 2J = –17.62 cm–1 for the adjacent NiII ions with a separation of 10.291(26) Å. The ferromagnetic coupling sign can be explained by the McConnell I spin‐polarization mechanism. 相似文献
17.
Phosphodiester Cleavage Promoted by an Asymmetric Dinuclear Zinc Complex: Synthesis,Structure, and Catalytic Activity
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The dinuclear ZnII complex [Zn2L(DNBA)2]BPh4 · EtOH ( 1 ) (DNBA = 3,5‐dinitrobenzonic acid) with an asymmetric dinuclear ligand, N‐4‐methyl‐homopiperazine‐N′‐[N‐(2‐pyridylmethyl)‐N‐2‐(2‐pyridylethyl)amine]‐1,3‐diamino‐propan‐2‐ol (HL), was synthesized and characterized. Single crystal X‐ray crystallographic analysis shows that the coordination around the two ZnII ions in 1 is significantly asymmetric, and the distance between both atoms is 3.426 Å, which is close to the Zn···Zn distance in related natural dinuclear metalloenzymes. Phosphodiesterase activity of Zn2L in situ formed from a 2:1 mixture of Zn2+ ion and HL was investigated using bis(4‐nitrophenyl) phosphate (BNPP) as substrate. The pH dependence of the BNPP cleavage in aqueous buffer media reveals a bell‐shaped pH‐kobs profile with an optimum at about pH 7.9, which is parallel to the formation of the dinuclear species Zn2L‐OH obtained from the potentiometric titration. The catalytic rate constant (kcat) is 6.30 × 10–4 s–1 at pH 7.9 and 25 °C, which is approx. 108‐fold higher than that of the uncatalyzed reaction. The homopiperazine bound deprotonated Zn‐OH group is responsible for the hydrolysis reaction. The possible mechanism for the BNPP cleavage promoted by Zn2L is proposed on the basis of kinetic and spectral analysis. 相似文献
18.
Metal(II) Ion Complexes with 5‐(Pyrazin‐2‐yl)‐2,4‐dihydro‐3H‐1,2,4‐triazole‐3‐thione; Synthesis,Structural Characterization,Acid‐base,and Complexing Properties in Solution
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Aleksander Kufelnicki Jolanta Jaciubek‐Rosińska Marta Sobiesiak Agata Paneth Julia Jezierska Elzbieta Budzisz 《无机化学与普通化学杂志》2017,643(16):1067-1074
The study reports the synthesis of complexes Co(HL)Cl2 ( 1 ), Ni(HL)Cl2 ( 2 ), Cu(HL)Cl2 ( 3 ), and Zn(HL)3Cl2 ( 4 ) with the title ligand, 5‐(pyrazin‐2‐yl)‐1,2,4‐triazole‐5‐thione (HL), and their characterization by elemental analyses, ESI‐MS (m/z), FT‐IR and UV/Vis spectroscopy, as well as EPR in the case of the CuII complex. The comparative analysis of IR spectra of the metal ion complexes with HL and HL alone indicated that the metal ions in 1 , 2 , and 3 are chelated by two nitrogen atoms, N(4) of pyrazine and N(5) of triazole in the thiol tautomeric form, whereas the ZnII ion in 4 is coordinated by the non‐protonated N(2) nitrogen atom of triazole in the thione form. pH potentiometry and UV/Vis spectroscopy were used to examine CoII, NiII, and ZnII complexes in 10/90 (v/v) DMSO/water solution, whereas the CuII complex was examined in 40/60 (v/v) DMSO/water solution. Monodeprotonation of the thione triazole in solution enables the formation of the L:M = 1:1 species with CoII, NiII and ZnII, the 2:1 species with CoII and ZnII, and the 3:1 species with ZnII. A distorted tetrahedral arrangement of the CuII complex was suggested on the basis of EPR and Vis/NIR spectra. 相似文献
19.
The syntheses of homo‐ and heteropentanuclear coordination compounds with the molecular formulae [MZn4(L)4(L′)6] (M = CoII or Zn; L = chloride or acac; L′ = 1,2,3‐benzotriazolate) are reported. These compounds display a highly symmetric coordination unit consisting of a central metal ion (M = CoII or Zn) which is octahedrally coordinated by 6 tridentate benzotriazolate‐type ligands via their N(2) donor atom. The benzotriazolate ligands span the edges of an imaginary tetrahedron thus providing four coordination sites at the corners of the tetrahedron, which are then filled by four zinc ions. The coordination shell of the latter are completed by bidentate acetylacetonate (acac) ligands or by chloride anions, respectively. The solid state structures of two homopentanuclear metal complexes, namely [Zn5(acac)4(bta)6]·4C6H12 ( 1 ) (acacH = acetylacetone; btaH = 1,2,3‐benzotriazole), and [Zn5Cl4(Me2bta)6]·2DMF ( 2 ) (Me2btaH = 5,6‐dimethyl‐1,2,3‐benzotriazole) were determined by single crystal X‐ray structure analysis. The heteropentanuclear metal complex [CoIIZn4Cl4(Me2bta)6]·2DMF ( 3 ) is isostructural with compound 2 . Compound 1 was synthesized from stoichiometric amounts of Zn(acac)2 and btaH employing dichloromethane as solvent. The synthesis of compound 2 requires addition of an auxiliary base to the DMF solution of anhydrous ZnCl2 and Me2btaH. For compound 3 a stoichiometric ratio of Co(NO3)2·6H2O, anhydrous ZnCl2 and Me2btaH was employed during synthesis. Phase purity of all compounds was proved by X‐ray powder diffraction (XRPD) analysis, IR spectroscopy, and elemental analysis. Crystal data: for 1 (C80H100N18O8Zn5): monoclinic, space group P21/c with a = 23.781(5) Å, b = 16.000(3) Å, c = 25.170(5) Å, β = 115.29(3)°, V = 8659(3) Å3, Z = 4, ρ = 1.357 g cm?3. For 2 (C54H62Cl4N20O2Zn5): cubic, space group with a = 23.367(3) Å, V = 12759(3) Å3, Z = 8, ρ = 1.553 g cm?3. For 3 (C54H62Cl4CoN20O2Zn4): cubic, space group with a = 23.443(3) Å, V = 12884(3) Å3, Z = 8, ρ = 1.532 g cm?3. 相似文献
20.
Raif Kurtaran Cengiz Arici Kaan C. Emregül Diner Ülkü Orhan Atakol Mustafa Tatekin 《无机化学与普通化学杂志》2003,629(9):1617-1621
A homo‐dinuclear NiII complex was prepared from 2, 6‐bis(3, 5‐dimethylpyrazolyl)pyridine (Me4‐bpp) and azide ions in nonaqueous media. It was characterized by single crystal X‐ray structural analysis, IR spectroscopy, and elemental analysis. In addition, the electrochemical properties of the compound were determined with cyclic voltammetry in DMF. The title compound crystallizes in the P21/n monoclinic space group, with unit cell parameters a = 8.978(1), b = 12.459(1), c = 17.764(1) Å, ß =100.603(3)°, V = 1953.0(3) Å3, Z = 2. The Ni2+ ion has a distorted octahedral environment involving three nitrogen atoms of the Me4‐bpp ligand, two nitrogen atoms from the bridged azide group, and one nitrogen atom from the terminal azide group. The Ni···Ni distance is 3.273(5) Å. 相似文献