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1.
1 INTRODUCTIONInthepastfew years ,anincreasinginteresthasbeen giventothemagnetic propertiesofmolecularcomplexescomprisingsimultaneouslylanthanideandtransitionmetalionswiththeaimofclarifyingtheroleoftheexchangeinteractionsbetween 3dand 4fmetalionsmodifying…  相似文献   

2.
两种有机磺酸配合物的合成、表征及与DNA键合性质   总被引:1,自引:0,他引:1  
李明田  黄俊  周璇  王成刚 《无机化学学报》2008,24(11):1794-1802
合成了2个新型有机磺酸配合物,[Cd(phen)2(ans)2]·H2O (1)和[Pb(phen)2(ans)2]·H2O (2) (phen=1,10-邻菲咯啉,ans=4-氨基-1-萘磺酸根),通过元素分析、红外光谱等对配合物进了表征,用X-射线单晶衍射方法测定了配合物的单晶结构。应用紫外-可见吸收光谱、荧光光谱及粘度测定方法研究了配合物与ctDNA的作用,发现2个配合物均以插入和氢键两种模式与ctDNA发生作用。  相似文献   

3.
The quadruply bonded complexes containing bridging acetate and polydentate phosphine ligands of the type Mo2(O2CCR3)XJ3-etp) (R = H, X = Br, 1; R = F, X = CI, 2; R = F, X = Br, 3; etp = Ph2PCH2CH2P(Ph)CH2CH2PPh2) were prepared by reactions of Mo2(O2CCR3)X2(PPh3)2 with etp in CH2X2. Their UV-vis and 31P{1H}-NMR spectra have been recorded, and the structure of 1 has been determined by X-ray crystallography. Crystal data for 1·2CH2Br2: space group P21/c, a = 13.924(7) Å, b = 21.157(4) Å, c = 14.427(5) Å, β = 101.82(3)°, V = 4159(2) Å3, Z = 4, with final residuals R = 0.0797 and Rw = 0.0793. The absorption wavelengths of the δ → δ* transitions and the chemical shifts and the coupling constants of the 31P{1H}-NMR spectra of these complexes are dependent on the natures of the halogen atoms and the acetate ligands.  相似文献   

4.
合成了2种新颖的配合物[M(ImH)6](tfbdc)(M=Co,Ni;tfbdc=2,3,5,6-四氟对二苯甲酸根;ImH=咪唑),并通过元素分析,红外光谱,热重分析,循环伏安及X-射线单晶结构分析对其结构及性质进行了表征。2个配合物[Co(ImH)6](tfbdc)(1)和[Ni(ImH)6](tfbdc)(2)都属单斜晶系,空间群为P21/c,且Z=2。每1个金属离子与来自6个咪唑分子的6个氮原子配位,形成八面体配位构型。独立组分,[M(ImH)6]2+阳离子和四氟对二苯甲酸阴离子之间通过两种氢键(N-H…O和C-H…F)连接形成了一种三维的超分子网络结构。  相似文献   

5.
配体C9H7R(R=CH2CH2CH3(1),CH(CH3)2(2),C5H9(3),CH2C6H5(4),CH2CH=CH2(5))分别与Ru3(CO)12在二甲苯或庚烷中加热回流,得到了6个双核配合物[(η5-C9H6R)Ru(CO)(μ-CO)]2(R=CH2CH2CH3(6),CH(CH3)2(7),C5H9(8),CH2C6H5(9),CH2CH=CH2(10))和[(η5-C9H6)(H3CH2C)CHCH(CH2CH3)(η5-C9H6)][Ru(CO)(μ-CO)]2(11)。通过元素分析、红外光谱、核磁共振氢谱对配合物的结构进行了表征,并用X-射线单晶衍射法测定了配合物6,9,10和11的结构。  相似文献   

6.
配体C9H7R(R=CH2CH2CH3 (1),CH2(CH3)2 (2),C5H9 (3),CH2C6H5 (4),CH2CH=CH2 (5))分别与Ru3(CO)12在二甲苯或庚烷中加热回流,得到了6个双核配合物[(η5-C9H6R)Ru(CO)(μ-CO)]2(R=CH2CH2CH3 (6),CH2(CH3)2 (7),C5H8 (8),CH2C6H5 (9),CH2CH=CH2 (10))和[(η5-C9H6)(H3CH2C)CHCH(CH2CH3)(η5-C9H6)] [Ru(CO)(μ-CO)]2 (11).通过元素分析、红外光谱、核磁共振氢谱对配合物的结构进行了表征,并用X-射线单晶衍射法测定了配合物6,9,1011的结构.  相似文献   

7.
分别合成了 [Co(3, 3-tri)(men)Cl][ZnCl4]、[Co(3, 3-tri)(cmen)Cl][ZnCl4] (3, 3-tri = N-(3-胺基丙基)-1, 3-丙二胺,men = N-甲基乙二胺,cmen = 1, 2-二胺基-丙烷) 2体系的部分配合物异构体,用单晶 X-射线衍射分析方法解析了2异构体的晶体结构。其中 [Co(3, 3-tri)(men)Cl][ZnCl4] 体系的一异构体Ⅰ的化学简式为 CoCl(C9H27N5)ZnCl4,晶体属正交晶系,空间群 Pca21,a = 16.788(2),b = 7.964(1),c = 14.416(2) 牛琕 =1927.3(4) ?,Dc = 1.747 g/cm3,Z = 4,F(000) = 1032,Mr = 506.91,R = 0.0352,wR =0.0935;[Co(3, 3-tri)(cmen)Cl]2+ 体系的一异构体Ⅱ的化学简式为 CoCl(C9H27N5)ZnCl4稨2O, 晶体属三斜晶系,空间群 P ,a = 9.511(3), b = 9.972(3),c = 11.694(3) 牛琣 = 68.367(5),b = 85.196(6),?= 86.580(5),V = 1026.9(5)?3,Dc = 1.698 g/cm3,Z = 2,F(000) = 536,Mr = 524.92,R = 0.0494,wR = 0.1180。两异构体中 Co3+ 为六配位,晶胞中对映体比例均为1:1。在配合物异构体Ⅰ和Ⅱ中,三元胺以经式排布,三元胺配体(3, 3-tri)仲胺上的氢相对于Cl分别处于顺位(syn-)和反位(anti-);二元胺配体氮(或邻位碳)取代的胺基氮原子(N*)与三元胺配体中的仲氮原子分别处于对位(trans(N*))和邻位(cis(N*))。  相似文献   

8.
Four cobalt supramolecular architectures with Hmtyaa(2-(5-methyl-1,3,4-thiadiazol-2-ylthio)acetic acid) ligand have been synthesized.[Co(mtyaa)2(H2O)4]·4(H2O)(1):triclinic,space group P1 with a = 6.7537(18),b = 8.591(2),c = 10.615(3) ,α = 96.495(4),β = 99.955(5),γ = 103.615(5)°,V = 581.9(3) 3,Z = 1,Mr = 581.52,Dc = 1.659 g/m3,μ = 1.158 mm-1,F(000) = 301,Rint = 0.0557,R = 0.0377 and wR = 0.1056 for 1854 observed reflections with Ⅰ 2σ(Ⅰ);{[Co(4,4'-bipy)(H2O)4]·2(mtyaa)·2(H2O)}n(2):triclinic,space group P1 with a = 7.669(2),b = 8.840(3),c = 11.521(4) ,α = 79.912(5),β = 73.954(5),γ = 86.612(6)°,V = 738.9(4) 3,Z = 1,Mr = 701.67,Dc = 1.577 g/m3,μ = 0.924 mm-1,F(000) = 363,Rint = 0.0636,R = 0.0498 and wR = 0.1311 for 2155 observed reflections with Ⅰ 2σ(Ⅰ);{[Co(4,4'-bipy)(mtyaa)(H2O)3](mtyaa)·2(H2O)}(3):monoclinic,space group Pc with a = 7.7832(17),b = 11.527(3),c = 31.483(7) ,β = 91.952(4)°,V = 2822.9(11) 3,Z = 4,Mr = 683.65,Dc = 1.609 g/m3,μ = 0.963 mm-1,F(000) = 1412,Rint = 0.0758,R = 0.0609 and wR = 0.1095 for 5841 observed reflections with I 2σ(I);{[Co(bpe)(mtyaa)2(H2O)2]}n(4):monoclinic,space group C2/c with a = 19.290(11),b = 12.027(7),c = 14.865(8) ,β = 125.648(8)°,V = 2802(3)3,Z = 4,Mr = 657.66,Dc = 1.559 g/m3,μ = 0.959 mm-1,F(000) = 1356,Rint = 0.0456,R = 0.0332 and wR = 0.0985 for 2299 observed reflections with Ⅰ 2σ(Ⅰ).  相似文献   

9.
Cobalt(Ⅱ) can form complexes with Hdbm in different environments. Hdbm reacted with cobalt nitrate to give complex 1 [Co(dbm)2·2H2O]. When complex 1 reacted with pyridine, α-stilbazole or 4,4′-bipyridine respectively, complex 2 [Co(DBM)2Py2] (Py=pyridine), 3 [Co(DBM)2Sbz2] (Sbz=α-stilbazole) or 4 [Co(DBM)2BPy]n was obtained in turn through metathetical reaction. The coordination modes are octahedral polyhedrons. In the crystal structures, the two dbms take the plane position and two other donor molecules take the axial position. CCDC: 196070 for complex 2; 186859 for complex 3.  相似文献   

10.
The synthesis of the perbrominated arsaboranes closo‐1,2‐As2B4Br4 ( 1 ) and closo‐1,2‐As2B10Br10 ( 2 ) occurs by co‐pyrolysis of B2Br4 and AsBr3 at 500 °C. Repeated fractionation of the sublimable products in vacuo yields both compounds in pure form. The X‐ray structure determination for orthorhombic closo‐1,2‐As2B4Br4 ( 1 ) [space group: Pbcn, a = 2345.48(17) pm, b = 627.31(4) pm, c = 1294.02(9) pm for Z = 8] and the corresponding phosphorus compound, monoclinic closo‐1,2‐P2B4Br4 ( 3 ) [space group: P21/n, a = 806.84(6) pm, b = 1247.96(9) pm, c = 974.91(7) pm, β = 90.493(3)° and Z = 4] confirmed that both 1 and 3 , consistent with their 14‐skeletal electron counts, adopt octahedral structures distorted from regular by two arsenic or phosphorus atoms in the 1,2‐positions. The shortest boron–boron bonds within the cluster frameworks are located between the boron atoms antipodal to the heteroatoms.  相似文献   

11.
The thermal reaction of Ru3(CO)12 ( 1 ) with salicylic acid, in the presence of triphenylphosphine, pyridine, or dimethylsulfoxide, afforded the dinuclear complexes Ru2(CO)4(μ‐O2CC6H4OH)2L2 ( 2 ) [L = PPh3 ( 2a ). C5H5N ( 2b ); (CH3)2SO ( 2c )]. Complex 2b was further reacted with the aromatic dimmines 2,2′‐dipyridine or 1,10‐phenanthroline to give the cationic diruthenium complexes [Ru2(CO)2(μ‐CO)2(μ‐O2CC6H4OH)(N∩N)2]+ ( 3 ) [(N∩N) = 2,2′‐dipyridine ( 3a ); 1,10‐phenanthroline ( 3b )], which were isolated as their tetraphenylborate salts. All five novel complexes were characterized spectroscopically and analytically. For 2a – 2b and 3a – 3b , single‐crystal X‐ray diffraction studies were also carried out.  相似文献   

12.
合成了Co23tricmenClZnCl423tri=N2胺乙基13丙二胺cmen=12二胺基丙烷体系中的部分配合物异构体解析了其中两异构体的晶体结构。其中晶体属单斜晶系空间群P21/ca=1.02112nmb=0.92082nmc=1.95004nmβ=97.9074°V=1.81617nm3Dc=1.803g·cm-3Z=4F000=1000.00μMoKα=29.66cm-1R=0.0317Rw=0.0923晶胞中含4个配合物阳离子4个ZnCl42-阴离子晶体属三斜晶系空间群a=0.9095318nmb=0.96942nmc=1.17712nmα=110.6694°β=92.2384°γ=91.2114°V=0.96973nm3Dc=1.750g·cm-3Z=2F000=520.00μMoKα=27.84cm-1R=0.0365Rw=0.0975晶胞中含2个配合物阳离子2个ZnCl42-阴离子及2个水分子。两异构体中Co3 为六配位其差异仅表现在二元胺cmen中甲基的取向不同。在结构单元中对映体的比例为1∶1。  相似文献   

13.
芳基取代的四甲基环戊二烯 C5HMe4Ar(Ar=Ph,4-CH3Ph,4-OCH3Ph,4-ClPh,4-BrPh) 分别与Re2(CO)10在二甲苯中加热回流,得到了5个单核配合物[(η5-C5Me4Ar)Re(CO)3](Ar=Ph (1),4-CH3Ph (2),4-OCH3Ph (3),4-ClPh (4),4-BrPh (5)]。通过元素分析、红外光谱、核磁共振氢谱对配合物1~5的结构进行了表征,用X射线单晶衍射法测定了配合物的结构。同时,研究了这五种配合物在芳香族化合物Friedel-Crafts烷基化反应中的催化活性。  相似文献   

14.
芳基取代的四甲基环戊二烯 C5HMe4Ar(Ar=Ph,4-CH3Ph,4-OCH3Ph,4-ClPh,4-BrPh) 分别与Re2(CO)10在二甲苯中加热回流,得到了5个单核配合物[(η5-C5Me4Ar)Re(CO)3](Ar=Ph (1),4-CH3Ph (2),4-OCH3Ph (3),4-ClPh (4),4-BrPh (5))。通过元素分析、红外光谱、核磁共振氢谱对配合物1~5的结构进行了表征,用X射线单晶衍射法测定了配合物的结构。同时,研究了这五种配合物在芳香族化合物Friedel-Crafts烷基化反应中的催化活性。  相似文献   

15.
Four Schiff base complexes, [Cu2(L1)2(μ‐NCS)2] ( 1 ), [Cu2(L2)2(μ‐N3)2] ( 2 ), Cu[Cu(CH3COO)(L3)]2 ( 3 ), and [Zn{Zn(C3H4N2)(L3)}2(NO3)](NO3) ( 4 ) (where L1 = 2‐[(pyridin‐2‐ylmethylimino)methyl]phenol, L2 = 1‐[(pyridin‐2‐ylmethylimino)methyl]naphthalen‐2‐ol, and L3 = bis(salicylidene)‐1, 3‐propanediamine), were synthesized and characterized by elemental analyses, infrared spectroscopy, and single crystal X‐ray determinations. Both 1 and 2 are structurally similar di‐nuclear complexes, which are located at crystallographic inversion centers (with the center of the central Cu2N2 ring). In 1 , each copper atom has a slightly distorted square pyramidal configuration, coordinated by two nitrogen atoms and one oxygen atom from L1 and another two terminal nitrogen atoms from two bridging thiocyanate anions. The Cu···Cu separation is 3.466(3) Å. The structure of 2 is similar to that of 1 , with Cu···Cu separation of 3.368(2) Å. Both 3 and 4 are linear tri‐nuclear complexes. In 3 , the central Cu2+ ion is located on an inversion centre and has a distorted octahedral coordination involving four bridging O atoms from two Schiff base ligands (L3) in the equatorial plane and one O atom from each bridging acetate group in the axial positions. The coordination around the terminal Cu2+ ions is irregular‐square pyramidal, with two O and two N atoms of L3 in the basal plane and one O atom from an acetate group in the apical position. The acetate bridges linking the central and terminal Cu2+ ions are mutually trans. The Cu···Cu separation is 3.009(3) Å. In 4 , the coordination configuration of the central and the terminal zinc atoms are similar to that of the 3 , with Zn···Zn separation of 3.153(4) Å. The three Schiff bases and the corresponding three copper complexes exhibit good antibacterial properties, while the zinc complex 4 has nearly no.  相似文献   

16.
应用遗传算法对二氧化硅团簇(SiO2)n(n≤20)的结构进行了优化计算。分析讨论了结构和结合能随团簇尺寸的变化规律,发现(SiO2)n团簇系列不存在明显的幻数,并在n≤20的范围内,不呈现出相应大块物质的结构特征,  相似文献   

17.
Although coordination polymers generally do not melt, several that do melt have been synthesized recently and have drawn much attention. In this study, two- and three-dimensional coordination polymers that melt were synthesized, [Ru(Cp)(C6H5R)][M{C(CN)3}2] (R=H, Me, Et; M=K, Rb; Cp=C5H5), which are complex salts comprising M[C(CN)3] and organometallic ionic liquids [Ru(Cp)(C6H5R)][C(CN)3]. They have anionic [M{C(CN)3}2]n coordination polymer frameworks, whose dimensionalities depend on the size of the organometallic cation inside. Their melting points decreased with increasing cation substituent length and size of the alkali metal ion (Tm=102–239 °C), and these low-melting-point coordination polymers exhibited incongruent melting, forming mixtures of solid M[C(CN)3] and ionic liquid upon melting. Using the same method, coordination polymers were synthesized with various bridging ligands, [Co(Cp)2][MX2] (X=B(CN)4, C(CN)3, N(CN)2; M=K, Na), as well as a paramagnetic coordination polymer, [Fe(Cp)2][K{C(CN)3}2].  相似文献   

18.
19.
用单晶 X-射线衍射分析方法解析了[Co(2,3-tri)(cmen)Cl][ZnCl4](2,3-tri=N-(2-胺基乙基)-1,3-丙二胺,cmen=1,2-二胺基-丙烷,化学简式:CoCl(C9H25N5)ZnCl4,Mr=492.88)体系中的 2个异构体的晶体结构。其中异构体m2[ZnCl4]晶体属单斜晶系,空间群P21/c,a=10.7741(2),b=15.3411(7),c=11.7710(3)A,β=100.928(3)°,V=1909.8(4)A3,Dc=1.714g/cm3,Z=4,F(000)=1000,R=0.0488,wR=0.1301,晶胞中含4个配合物阳离子,4个[ZnCl4]2-阴离子;异构体m4'[ZnCl4]晶体属三斜晶系,空间群P1,a=8.8472(5),b=10.0484(7),c=11.9139(9)A,α=90.456(3),β=99.972(3)°,γ=112.836(3)°,V=957.8(3)A3,Dc=1.709g/cm3,Z=2,F(000)=520,R=0.0493,wR=0.1174,晶胞中含有2个配合物阳离子,2个[ZnCl4]2-阴离子。两异构体中Co3+为六配位。在结构单元中对映体的比例均为1:1。  相似文献   

20.
The synthesis and crystal structure of the novel reduced molybdenum oxide Mg4.5Pr79.5Mo126O312 are presented. This compound crystallizes in the trigonal space group R-3 m with a = 11.3061(2) Å, c = 58.242(1) Å, V = 6447.5(2) Å3, and Z = 1. Refinements yield R(F 2) = 0.0433 and wR(F 2) = 0.0931 for 2827 unique reflections. The structure is built up from alternating slabs made up of molybdenum forming Mo3, Mo7 and Mo19 clusters, praseodymium and oxygen atoms, and slabs containing isolated MoO6 octahedra. The Pr3+ cations are localized either within the slabs or at their borderlines to ensure the cohesion between the slabs. Of the six crystallographically independent sites occupy by the Pr3+ cations, two of them also contain randomly about 15% and 20% of Mg2+ cations while the remaining four are fully occupied by the Pr3+ cations.  相似文献   

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