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1.
The metal complexes [Hg2(tbim)2Br4]·2DMF ( 1 ) and [Hg2(tbim)I4]·1.5DMF ( 2 ) were prepared by reactions of 1,3,5‐tris(benzimidazol‐1‐ylmethyl)‐2,4,6‐trimethylbenzene (tbim) with HgBr2, HgI2, respectively, and [Hg2(tbim)I4]·0.5(FeCp2)·H2O ( 3 ) was obtained by the same method with addition of ferrocene (FeCp2) as additive. Their structures were determined by X‐ray crystallographic analyses. Complex 1 has a macrocyclic binuclear structure with one benzimidazole arm of the ligand free of coordination and the binuclear units are further connected by C‐H···N hydrogen bonds to give an infinite zigzag chain. Complexes 2 and 3 have a 2D network structure in which tbim serves as a tridentate ligand. The results showed that the halides of bromide and iodide have remarkable impact on the structure of the complexes. The FeCp2 molecules are trapped in the voids of framework 3 .  相似文献   

2.
The thermodynamic functions of the complexation of Ag(I) by the tripodal ligands, tris(2-(methylamino)ethyl)amine (Me3tren) and tris(2-(dimethylamino)ethyl)amine (Me6tren) (L), are determined in dimethyl sulfoxide (DMSO) by potentiometric and calorimetric techniques at 298.0 K and 0.1 mol⋅dm−3 ionic strength (Et4NClO4). A comparison is made between previous data concerning Ag(I) complex formation with the non-alkylated tripodal 2,2′,2″-triaminotriethylamine (tren), in order to analyze the influence of N-methylation on this type of branched donor, and with those relative to the linear triethylenetetramine (trien) and 1,1,4,7,10,10-hexamethyltriethylenetetramine (Me6trien). The results are discussed taking into account different σ-donating properties, geometric arrangement of the ligands, steric repulsions and solvation effects.  相似文献   

3.
Two new dithioether ligands, 1,4‐bis[(phenylsulfanyl)methyl]naphthalene ( L1 ), and 4,4′‐bis[(tert‐butylsulfanyl)methyl]biphenyl ( L2 ) were synthesized and their silver(I) complexes were studied. Both AgI complexes, [Ag L1 (NO3)]n ( 1 ) and [Ag L2 (NO3)]2 ( 2 ), were synthesized at ambient temperature and characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction analysis. Single‐crystal X‐ray analysis shows that complex 1 has a one‐dimensional helical chain structure with the neutral repeating unit [Ag(μ2‐ L1 )(NO3)], whereas complex 2 has a centrosymmetrical neutral dinuclear structure. Moreover, complexes 1 and 2 are further extended into three‐dimensional supramolecular frameworks by hydrogen bonding and π–π stacking interactions, respectively. In addition, complexes 1 and 2 display strong blue emission in the solid state at room temperature.  相似文献   

4.
Four new bridged silver(I) complexes, namely [Ag22‐teda)(μ2‐fbc)2] ( 1 ), [Ag22‐1,6‐dah)2](bpdc) · 4H2O ( 2 ), [Ag22‐2‐ap)(2‐ap)(bnb)] · 0.34H2O ( 3 ), [Ag22‐pyc)2(2‐apy)2] · 0.5H2O ( 4 ), have been synthesized and characterized by elemental analysis and crystallographic methods [fbc = 4‐fluorobenzoate, teda = triethylenediamine ( 1 ); bpdc = biphenyl‐4,4′‐dicarboxylate, 1,6‐dah = 1,6‐diaminohexane ( 2 ); bnb = 3,5‐binitrobenzoate, 2‐ap = 2‐aminopyrimidine ( 3 ); pyc = 3‐pyridinecarboxylate acid, 2‐apy = 2‐aminopyridine ( 4 )]. Complex 1 contains a 1D linear chain paralleling to the c‐axis, whereas in complex 2 silver(I) atoms were bridged by the 1,6‐dah ligand into a zigzag chain, further giving a 1D ribbon by weak Ag ··· Ag interactions. Complex 3 consists of a dinuclear silver(I) [Ag22‐2‐ap)(2‐ap)(bnb)] moiety and a lattice water molecule, forming a 3D network via a number of hydrogen‐bonding interactions such as N–H ··· O, N–H ··· N and C–H ··· O hydrogen bond and other weak interactions such Ag ··· Ag, Ag ··· N, N ··· O as well as O ··· O interaction. Similar to 3 , the asymmetric unit of 4 consists of one dinuclear silver(I) [Ag22‐pyc)2(2‐apy)2] moiety and half lattice water molecule, further generating a tetranuclear silver(I) {[Ag22‐pyc)2(2‐apy)2]2 · H2O} moiety. These moieties construct a 3D supramolecular network structure of 4 through N–H ··· O, O–H ··· O and C–H ··· O hydrogen bonds as well as other weak interactions such as Ag ··· O and N ··· O interactions.  相似文献   

5.
Tris{2‐[ N ‐(diethylaminothiocarbonyl)benz(‐amidino; imidoxy; ‐imidothio)‐ N ′‐yl]ethyl}amines – New Tripodal Ligands. Synthesis, Complex Stability, and Extraction Behaviour of their Silver(I) Complexes N‐(Thiocarbamoyl)‐benzimidoylchlorides react with trivalent nucleophiles to give four novel tripodal ligands. Two of them have been characterized by X‐ray methods. The ligands form with silver(I) cationic mononuclear complexes in which the three arms of the ligand are coordinated monodentately via sulfur. The results of FAB and ESI mass spectrometry as well as ESCA and NMR investigations verify this binding mode. The protonation constants of the ligands and the stability constants of silver(I) complexes have been determined potentiometrically. The novel tripodal compounds behave as powerful extractands for silver(I).  相似文献   

6.
Three new complexes with phosphanylphosphido ligands, [Cu4{μ2‐P(SiMe3)‐PtBu}4] ( 1 ), [Ag4{μ2‐P(SiMe3)‐PtBu2}4] ( 2 ) and [Cu{η1‐P(SiMe3)‐PiPr2}2][Li(Diglyme)2]+ ( 3 ) were synthesized and structurally characterized by X‐ray diffraction, NMR spectroscopy, and elemental analysis. Complexes 1 and 2 were obtained in the reactions of lithium derivative of diphosphane tBu2P‐P(SiMe3)Li · 2.7THF with CuCl and [iBu3PAgCl]4, respectively. The X‐ray diffraction analysis revealed that the complexes 1 and 2 present macrocyclic, tetrameric form with Cu4P4 and Ag4P4 core. Complex 3 was prepared in the reaction of CuCl with a different derivative of lithiated diphosphane iPr2P‐P(SiMe3)Li · 2(Diglyme). Surprisingly, the X‐ray analysis of 3 revealed that in this reaction instead of the tetramer the monomeric form, ionic complex [Cu{η1‐P(SiMe3)‐PiPr2}2][Li(Diglyme)2]+ was formed.  相似文献   

7.
Compounds of general formula Au{SSi(OR)3}(PPh3), R = Pri ( 1 ), Bus ( 2 ) or But ( 3 ), have been obtained by reaction of AuCl(PPh3) with triethylammonium salts of respective silanethiols, (RO)3SiSH. Molecular and crystal structures of 1 , 2 , and 3 have been determined by the single crystal X‐ray structural analysis. Compounds 1 and 2 are the first structurally characterized metal derivatives of hydrolytically unstable trialkoxysilanethiols (PriO)3SiSH and (BusO)3SiSH.  相似文献   

8.
The reaction of [(Ph3P)2CuCl]2 with 4‐amino‐6‐methyl‐1,2,4‐triazine‐thione‐5‐one (AMTTO, 1 ) in methanol and further recrystallization from methanol/acetone solution gives [(C4H4N3SON(=CMe2)Cu(PPh3)2Cl] ( 2 ) as a neutral complex. [(C4H4N3SON(=CMe2)Ag(PPh3)2]NO3 ( 4 ) can be obtained in excellent yield by the reaction of [(AMTTO)2Ag]NO3 ( 3 ) with triphenylphosphane in methanol/acetone. Both complexes were characterized by infrared spectroscopy, elemental analyses as well as by X‐ray diffraction studies. Crystal data for 2 at –80 °C: space group P1 with a = 1233.8(1), b = 1389.7(1), c = 1417.1(1) pm, α = 89.36(1)°; β = 65.10(1)°, γ = 65.95(1)°, Z = 2, R1 = 0.0582 and for 4 at –80 °C: space group P1, with a = 1193.3(1), b = 1308.5(1), c = 1385.3(1) pm, α = 94.69(1)°, β = 109.14(1)°, γ = 93.42(1)°, Z = 2, R1 = 0.0716.  相似文献   

9.
Starting from the tripodal tetradentate ligands ‐(3,5‐dibromo‐2‐hydroxybenzyl)(2‐hydroxybenzyl)(2‐pyridyl)methylamine (H2L1), (3,5‐dibromo‐2‐hydroxybenzyl)(2‐hydroxy‐5‐nitrobenzyl)(2‐pyridyl)methylamine (H2L2), and (3,5‐dichloro2‐hydroxybenzyl)(2‐hydroxy‐5‐nitrobenzyl)(2‐pyridyl)methylamine (H2L3) the new isostructural dinuclear zinc compounds [Zn2(L1)2]·N(CH2CH3)3 ( 1 ), [Zn2(L2)2]·2CH3OH ( 2 ) and [Zn2(L3)2]·C4H10O ( 3 ) were synthesized. Due to their enzyme‐like trigonal bipyramidal N2O3 coordination environment of the zinc ions and the similar Zn···Zn distances the complexes can be considered to be structural models for the active sites in phospholipase C and nuclease P1. With H2L3 also the dinuclear complex [Co2(L2)2(CH3OH)]·2CH3OH·0.5C4H10O ( 4 ) could be prepared. The new compounds were isolated and characterized by single crystal X‐ray crystallography as well as infrared spectroscopy. The cobalt compound 4 was additionally characterized by UV‐Vis spectroscopy and magnetic measurements. 1 crystallizes in the monoclinic space group P21/n with a = 11.2814(2), b = 28.6154(2), c = 13.1866(3) Å, β = 96.995(1)°, V = 4225.2(2) Å3, Z = 4. 2 and 3 are monoclinic, space group C2/c with a = 23.084(5), b = 9.232(2), c = 21.849(4) Å, &β; = 96.83(3)°, V = 4623(2) Å3, Z = 4, and a = 22.7834(3), b = 9.2463(1), c = 21.6351(3) Å, &β; = 97.592(1)°, V = 4517.7(2) Å3, Z = 4, respectively. 4 crystallizes in the monoclinic space group I2/a with a = 22.4680(4), b = 20.5517(4), c = 22.8910(6) Å, &β; = 111.938(1)°, V = 9804.7(4) Å3, Z = 8. 4 shows an effective magnetic moment of 6.72 μB at 300 K which clearly indicates the presence of two cobalt(II) high spin ions with Curie‐Weiss behaviour above 80 K. At lower temperatures a decrease of the effective magnetic moment was observed.  相似文献   

10.
The iron(III) complexes of the tripodal benzimidazole‐containing ligands tris(2‐benzimidazolylmethyl)amine (ntb), bis(2‐benzimidazolylmethyl)(2‐hydroxyethyl)‐amine (bbimae) and tris(5,6‐dimethyl‐2‐benzimidazolylmethyl)amine (me2ntb) are structural and functional models for intradiol cleaving catechol dioxygenases. The complexes [Fe(ntb)Cl2]Cl · 3 CH3OH ( 1 ; P 1, a = 9.830(2) Å, b = 12.542(3) Å, c = 13.139(3) Å, α = 82.88(3)°, β = 73.45(3)°, γ = 85.53(3)°, V = 1539.2(6) Å3; Z = 2) and [Fe(bbimae)Cl2]Cl ( 2 ; P21/n, a = 7.461(2) Å, b = 18.994(5) Å, c = 14.515(4) Å, β = 98.22(2)°, V = 2035.8(9) Å3, Z = 4) have been characterized by X‐ray crystallography and spectroscopic methods. In the octahedrally coordinated complexes two cis coordination sites – essential for catechol binding – are occupied by chloride ligands. The significant intradiol cleaving catechol dioxygenase activity of the model complexes was examined using 3,5‐di‐tert‐butylcatechol as a substrate.  相似文献   

11.
通过含2-噁唑啉基三角架配体1,3,5-三(2-噁唑啉基)苯(L)与三氟醋酸银反应合成了配合物[Ag4(L)2(CH3CN)2(CF3CO2)4]n (1), 并利用元素分析、电喷雾质谱、X射线单晶衍射等方法对其进行了表征. 晶体结构解析结果显示配合物1属三斜晶系, 空间群P-1, a=0.83731(6) nm, b=1.22828(9) nm, c=1.33997(10) nm, α=102.9760(10)°, β=107.3050(10)°, γ=93.8600(10)°, Z=1, R=0.0365, wR2=0.0929. 该配合物是由[Ag4(L)2(CF3CO2)2]2+笼状结构单元通过另外两个三氟醋酸根双桥连形成的一维链状结构. 相邻的链间通过C—H…O氢键进一步扩展为二维网状结构. 电喷雾质谱研究结果显示在实验条件下, 溶液中配合物1是以聚合状态存在的.  相似文献   

12.
Two coordination polymers [Ag(dach)]n(NO3)n ( 1 ) and [Ag(teda)(F3CSO3)]n ( 2 ) (dach = 1, 2‐diaminocyclohexane, teda = 1, 4‐diazabicyclo[2.2.2]octane) have been synthesized and characterized by X‐ray single crystal analysis and cytotoxicity investigation. Compound 1 has a one‐dimensional chain‐like structure which is extended by ligand unsupported Ag···Ag interactions, hydrophobic interaction and hydrogen bonds into a three‐dimensional supramolecular array while compound 2 shows three‐dimensional diamond‐like framework constructed by coordination bonds. The high cytotoxities of these two compounds imply that they are potential candidates for antitumor agents.  相似文献   

13.
1,2-二(2-胺基苯氧基)乙烷银配合物的合成与晶体结构   总被引:1,自引:0,他引:1  
本文采用配体1, 2-二(邻氨基苯氧基)乙烷(L)分别与AgPF6, AgCF3SO3, AgNO3和AgSbF6 进行配位反应,依次得到了四个配合物1 [Ag2(L)2(PF6)]、2 [Ag2(L)2(CF3SO3)2]、3 [Ag(L)NO3]n 和4 [Ag(L)2SbF6]n,并通过FTIR、元素分析、以及X射线单晶衍射等对配合物的结构与组成进行了表征。单晶衍射结果表明,配合物1和2为双核银(I)配合物,3和4为银(I)的配位聚合物。配合物1具有穴状结构,2经Ag?Ag键桥连两个配体形成扭曲的非平面结构。聚合物3的结构为一维(1D)“之”字链,4具有三维(3D)多孔的结构框架。在四个配合物结构中,相应的抗衡阴离子均未参与Ag(I)进行配位作用。  相似文献   

14.
The coordination polymers [Cu2(tpim)2] · 2H2O ( 1 ) and [Co(H2tpim)2(MoO4)2] ( 2 ) [Htpim = 2,4,5‐tri(4‐pyridyl)‐imidazole] were synthesized. Their structures were determined by single‐crystal X‐ray diffraction and further characterized by elemental analyses, IR spectroscopy, and TG analyses. Compounds 1 and 2 both contain chiral helical‐layer structures. Compound 1 exhibits a novel 3D (3,3,4)‐connected framework with (4 · 6 · 8)(6 · 82)(4 · 6 · 83 · 10) topology, which is constructed from left‐ and right‐ helices. Compound 2 displays a 2D chiral helical‐layer structure which can be rationalized as a (3,6)‐connected 2D kgd (kagome dual) net, and these 2D layers are further extended by hydrogen‐bonding interactions to form a 3D supramolecular network. By comparing compounds 1 and 2 , it is believed that the tripodal N‐containing ligand (Htpim) plays a key role in the construction of helical coordination polymers. In addition, the photoluminescence property of compound 1 and the magnetic property of compound 2 were studied.  相似文献   

15.
Large silver(I) clusters stabilized by the dianionic carba-closo-dodecaboranylethynyl ligand were obtained. Crystallization of polymeric {Ag2(12-C≡C-closo-1-CB11H11)}n from dimethyl sulfoxide afforded [Ag14(12-C≡C-closo-1-CB11H11)7(DMSO)12] · DMSO that contained an AgI10 cage augmented by four AgI ions. Crystals of [Ag16(12-C≡C-closo-1-CB11H11)8(THF)12] · 2THF were obtained from anhydrous THF and {Ag2(12-C≡C-closo-1-CB11H11)}n. In the presence of moisture the similar but water-containing complex [Ag16(12-C≡C-closo-1-CB11H11)8(THF)12(H2O)2] · 2.5THF was identified. Both silver(I) clusters are composed of a central octahedral AgI6 unit and ten further silver(I) ions bonded via argentophilic interactions. [Ag14(12-C≡C-closo-1-CB11H11)7(DMSO)12] · DMSO and [Ag16(12-C≡C-closo-1-CB11H11)8(THF)12] · 2THF were characterized by elemental analysis and vibrational (IR and Raman) as well as NMR spectroscopy. In addition, the crystal structures of [Ag25(12-C≡C-closo-1-CB11H11)12(CH3CN)13.5(OH)] · 0.5CH3CN and [Ag25(12-C≡C-closo-1-CB11H11)12{(CH3)2CO}13.5(H2O)Cl] · 15(CH3)2CO were determined. Both compounds contain AgI14 rhombic dodecahedrons augmented by eleven silver(I) ions. A hydroxide or a chloride template ion is present in the center of the rhombic dodecahedron, respectively.  相似文献   

16.
The reaction of 4-amino-6-methyl-1,2,4-triazine-3(2 H)-thione-5-one (AMTTO) with silver(I) nitrate in methanol gives the complex [Ag(AMTTO)2]NO3 ( 1 ). 1 was characterized by IR and 13C NMR spectroscopy and by an X-ray structure analysis [space group C2/c, Z = 4, lattice dimensions at –80 °C: a = 1306.7(2), b = 1139.0(2), c = 1089.2(1) pm, β = 94.54(1)°, R1 = 0.0294]. The cation possesses a highly distorted linear coordination sphere in the solid state.  相似文献   

17.
The ditopic ligand 1, 2‐bis(benzimidazol‐1‐ylmethyl)benzene (L1) as well as its silver(I) complexes [Ag2L12(CF3CO2)2] ( 1 ) and [Ag2L12](CF3SO3)2 · (L1) · 2H2O · 0.5C2H5OH ( 2 ) were prepared and structures characterized by X‐ray crystallography. The AgI atoms in 1 are trigonally coordinated by two NBIm atoms from the arms of L1 and by one O atom of the anion CF3CO2, while those in 2 are only linearly ligated by NBIm. Different silver salts of CF3CO2 and CF3SO3 lead to different configurations of the dimeric unit [Ag2L12]2+: chair‐form in ( 1 ) but boat‐form in ( 2 ). The discrete molecules in both 1 and 2 are assembled into network structures through face‐to‐face π · · · π stacking and edge‐to‐face C—H · · · π interactions in the crystalline state, as well as N—H · · · O and C—H · · · O hydrogen bonds. Solution 1H NMR studies showed the formation of one sole species in solution or a rapid equilibrium was established on the NMR time scale at room temperature.  相似文献   

18.
Crystal structures of a series of manganese(I) complexes containing tripodal ligands were determined. For [η3-{CH3C(CH2PPh2)2(CH2SPh)-P,P′,S}Mn(CO)3]PF6 ( 1 ): a = 10.856(3) Å, b = 19.698(3) Å, c = 17.596(5) Å, β = 96.17(2)°, monoclinic, Z = 4, P21/c, R(Fo) = 0.068, Rw(Fo) = 0.055 for 3617 reflections with Io > 2σ(Io). For [η3-{CH3C(CH2PPh2)(CH2SPh)2-P,P′,S}Mn(CO)3]PF6 ( 2 ): a = 9.890(2) Å, b = 20.403(4) Å, c = 10.269(3) Å, β = 117.44(2)°, monoclinic, Z = 2, P2l, R(Fo) = 0.050, Rw(Fo) = 0.037 for 1760 reflections with Io > 2σ(Io). For [η3-{CH3C(CH2PPh2)2(CH2S)-P,P′,S}Mn(CO)3] ( 4 ): a = 8.191(7) Å, b = 10.495(3) Å, c = 19.858(6) Å, α = 99.61(2)°, β = 96.17(2)°, γ = 92.70(4)°, triclinic, Z = 2, P-I, R(Fo) = 0.048, Rw(Fo) = 0.039 for 2973 reflections with Io > 2σ(Io). There is no significant difference in the bond lengths of Mn-S bonds among three species in their crystal structures [2.325(2) Å in 1; 2.358(4) in 2; 2.380(2) in 4], but the better donating ability of thiolate in complex 4 appears on the lower frequencies of its carbonyl stretching absorptions.  相似文献   

19.
设计合成了同时含有丙腈基和咪唑基的新型三脚架配体N,N-二(3-丙腈基)-[3-(1-咪唑基)]正丙胺(L),并与银盐按1:1和2:1的比例反应分别得到了配合物{[AgL]X}n (X = BF4-,1a;X = ClO4-,1b)和{[Ag(L)2]ClO4}n(2),并用X-射线单晶结构分析和电喷雾质谱等方法对其进行了表征。结构分析结果表明,配合物1a和1b为一维链状结构,而配合物2则为单核结构。表明金属盐和配体的比例对配合物结构有很大影响。  相似文献   

20.
The reactions of the cycloaurated gold(III) complexes (2-bp)AuCl2 (2-bp = 2-benzylpyridyl) or (damp)AuCl2 (damp = Me2NCH2C6H4) with an excess of sodium saccharinate (Nasacc), potassium phthalimidate (Kphth), or with isatin and trimethylamine in refluxing methanol results in the successful isolation of a series of new gold(III) imidate complexes. These were characterised by NMR and IR spectroscopies, and by X-ray structure determinations on (2-bp)Au(sacc)2 and (2-bp)Au(phth)2. In both structures, the planes of the saccharinate and the phthalimidate ligands are orientated almost perpendicular to the gold coordination plane. As expected from trans-influence considerations, the Au–N(imidate) bond lengths trans to the aryl carbon atoms are longer than the Au–N(imidate) bond lengths trans to the pyridyl groups. The complexes have also been characterised by electrospray ionisation MS; in the presence of halide ligands, one imidate ligand is readily displaced. Anti-tumour (P388 murine leukemia) and selected anti-microbial data for the new complexes are reported. Surprisingly, all three damp complexes had low anti-tumour activity, which is likely to be a consequence of the poor solubility of these complexes. The synthesis and characterisation of a related gold(III) bis(amidate) complex derived from sulfathiazole is also described.  相似文献   

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