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1.
《Journal of organometallic chemistry》2003,665(1-2):167-175
Reactions of Sallyl systems (allyl sulphides of RSallyl type, where R=Et, allyl, Ph, Me3C, Ph3C, as well as of allyl phenyl sulphoxide, allyl phenyl sulphone, 2,5-dihydro-1,1-dioxothiophene) with [RuClH(CO)(PPh3)3] and other ruthenium compounds have been investigated. Double-bond migration was observed in the case of allyl trityl sulphide, allyl t-butyl sulphide and both sulphones, that is, where co-ordinating properties of sulphur were not too strong. High-yielded syntheses of (E)- and (Z)-RSCHCHCH3 (R=Me3C, Z:E=96:4 and Ph3C, Z:E=92:8), (E)PhS(O2)CHCHCH3 and 2,3-dihydro-1,1-dioxothiophene from respective allyl systems are described. The binuclear Ru complex, formed in the model reaction of allyl phenyl sulphide with [RuClH(CO)(PPh3)3] has been isolated and its structure has been resolved. The mechanism of the reaction between Sallyl systems and [RuClH(CO(PPh3)3] is proposed. 相似文献
2.
Summary The complex [Rh2Cl2(-CO)(-vdpp)2] (1) (vdpp=H2C=C(PPh2)2) was prepared by reaction of [Rh2(CO)4-(-Cl)2] with vdpp. When (1) is allowed to stand overnight under an atmosphere of CO without stirringtrans-[Rh2Cl2(CO)2(-vdpp)2] is formed as a red precipitate in low yields. On rapid addition of CO the tricarbonyl complex [Rh2(CO)2(-CO)(-Cl)(-vdpp)2]-Cl is formed instead. The chemical behaviour of the vdpp-substituted complex (1) is very similar to that of the corresponding dppm-substituted complex [Rh2(Cl2-(-CO)(-dppm)2] (dppm=H2C(PPh2)2). this similarity also extends to the molecular structures of both compounds. Unit cell parameters of (1): space group Pben (Z=8),a=2344.7(5),b=1506.9(7),c=3021.6(9)pm. Rh-Rh 267.4(1) pm. 相似文献
3.
《Journal of Coordination Chemistry》2012,65(12):1317-1325
Two Zn(II) complexes, [Zn(Fura)2(2,2′-bpy)(H2O)] (1) and [Zn(µ-dnbc)2] (2), have been synthesized and characterized by X-ray diffraction and IR spectra. 1 is a quaternary Zn(II) complex with ZnN2O3 configuration distorted square pyramid geometry; 2 is a Zn(II) coordination polymer with 1D double-helical chains bridged by 3,5-dinitrobenzoic acid. 相似文献
4.
《Journal of Coordination Chemistry》2012,65(6):882-890
Lead(II) 4,4,4-trifluoro-1-phenyl-1,3-butandionate (TFPB?) complexes with 1,10-phenanthroline (phen) and 2,2′-bipyridine (2,2′-bipy), [Pb(L)(TFPB)2], have been synthesized and characterized by elemental analysis, IR-, 1H NMR spectroscopy and studied by X-ray crystallography. The self-assembly of [Pb(L)(TFPB)2] complexes, (L?=?phen or 2,2′-bipy) is caused by C–H?···?F–C, C–H?···?O–C and π–π stacking interactions. The thermal stabilities of compounds were studied by thermal gravimetric (TG) and differential thermal analyses (DTA). 相似文献
5.
L. A. Glinskaya R. F. Klevtsova T. G. Leonova S. V. Larionov 《Journal of Structural Chemistry》2000,41(1):161-165
While seeking molecular precursors for ZnS films obtained by gas phase chemical deposition [1, 2] we synthesized mixed-ligand
compounds ZnL(ROCS2)2 [R = i-Pr. /-Bu; L = 2,2′-bipyridyl (2,2′-Bipy), 1,10-phenanthroline (Phen)] [3]. The volatile complex Zn(2,2′-Bipy)(i-PrOCS2)2 was used as a precursor to obtain electroluminescent ZnS:Mn films [4]. According to XRD data, the compound Zn(Phen)(i-BuOCS2)2 is monomeric. The c.n. of zinc is six. The Phen and 1-B11OCS2 ions behave as cyclic bidentate ligands [3, 5]. It was assumed that other mixed-ligand complexes with Phen and 2,2′-Bipy
have an analogous structure [3]. Here we report on the structure of the known mixed-ligand complex of zinc(II) ethylxanthate
with 2,2′-bipyridyl [6, 7]. It was found that the behavior of alkylxanthate ligands in mixed-ligand complexes of zinc(II)
is more complex.
Translated from Zhumal Stmktumoi Khimii, Vol. 41, No. 1, pp. 196-201, January–February, 2000. 相似文献
6.
Géraldine Poignant Sourisak Sinbandhit Loïc Toupet Véronique Guerchais 《Angewandte Chemie (International ed. in English)》1998,37(7):963-965
The electrophilic iron–carbene chelate complexes 1 and 2 react with alkoxides RO− to give the neutral chelate complex 3 and the carbene complex 4 , respectively. Depending on the nature of the chelating ortho substituent, selective activation of the Ar–Cl or Ar–C bond occurs; these processes are promoted by the chelation. 相似文献
7.
1 INTRODUCTION o-Phthalic acid (H2pht) is a versatile ligand for co-ordinating to metal ions in various modes, such asmonodentate bonding through a carboxylic O atom[1],bidentate fashion via two carboxylic O atoms[2] andtriple coordination through its three carboxylic Oatoms[3], and bridging mode with two or four Oatoms of its carboxylate groups[4]. The coordinationproperties thus allow for the preparation of complex-es with a large variety of architectures, forming iso-lated mono-, di… 相似文献
8.
The substitution behaviour of [Pt(terpy)H2O]2+ and [Pt(bpma)H2O]2+, where terpy is 2,2:62-terpyridine and bpma is bis(2-pyridylmethyl)amine, was studied as a function of entering thiol concentration and temperature. The reactions between the Pt-complexes and DL-penicillamine, L-cysteine and glutathione were carried out in a 0.10 mol dm–3 aqueous HClO4 medium using stopped-flow and conventional u.v.–vis spectrophotometry. The observed pseudo-first-order rate constants for the substitutions are given by k
obs = k
2[thiol] + k
–2. The k
–2 term represents the reverse solvolysis. This was found to be zero for PtII(terpy) which was the most reactive complex. The second-order rate constants, k
2, for the three thiols varied between 0.107 ± 0.001 and 0.517 ± 0.025 M–1 s–1 for PtII(bpma) and 10.7 ± 0.7–711.9 ± 18.3 M–1 S–1 for PtII(terpy), whereas glutathione was found to be the strongest nucleophile. An analysis of the activation parameters, H
and S
, clearly shows that the substitution process is associative in nature. 相似文献
9.
The compounds [C4H8ON(C3H5)2]+[Cu4Cl5]– (I), [C4H8ONH(C3H5)]+[CuBr2]– (II), and [C4H8ONH(C3H5)]+[CuBr1.41Cl0.59]– (III) were prepared for the first time by ac electrochemical synthesis from mono- and di-N-allyl derivatives of morpholinium and copper(I) halides in ethanol solution and structurally characterized. In the structure of I π-complex, the centrosymmetric Cu8Cl10 fragments are associated into layers perpendicular to the b axis. The N,N"-diallylmorpholinium cation functions as a bridge, which coordinates two copper atom of the adjacent inorganic fragments by both allyl groups. The trigonal-pyramidal surrounding of the Cu(I) atom, as well as the distorted tetrahedral coordination sphere of Cu(2), involves three chlorine atoms and the C=C bond, whereas the planar trigonal surrounding of the Cu(3) atom and trigonal-pyramidal surrounding of the Cu(4) atom involve only chlorine atoms. In the isostructural II and III σ-complexes, the edge-shared CuX4 tetrahedra form the infinite copper-halide chains running along the a axis. The inorganic fragments and organic N-allylmorpholinium cations are united into the three-dimensional crystal structures by N–H···X and C–H···X (X = Cl, Br) hydrogen bonds. 相似文献
10.
Three new tin coordination compounds (4,4'-Hbipy)2[Sn2(C2O4)3] ( 1 ), (4,4'-H2bipy)[Sn(C2O4)2] ( 2 ), and SnCl2(4,4'-bipy) ( 3 ) were synthesized under hydro-(solvo-)thermal conditions and their crystal structures were determined by single-crystal X-ray diffraction. Compound 1 exhibits a ionic structure based on discrete [4,4'-Hbipy]+ cations and [Sn2(C2O4)3]2– anions. These two units are linked via N–H ··· O hydrogen bonds to form a pseudo-one-dimensional zigzag hydrogen-bonded chain. In compound 2 , four-coordinate Sn atoms form monomeric tin dioxalato complexes, which are connected to the doubly protonated [4,4'-H2bipy]2+ cations through N–H ··· O hydrogen bonded to give a one-dimensional zigzag hydrogen-bonded chain. Compound 3 forms a three-dimensional hydrogen-bonded network, in which 1∞[SnCl2(4,4'-bipy)] linear chains are interconnected to each other by C–H ··· Cl hydrogen bonding. The solid-state UV/Vis/NIR diffuse reflectance spectroscopy shows that three compounds are broadband semiconductors. The thermogravimetric analysis evidences the thermal stability of the three compounds up to 175, 201, and 246 °C, respectively. 相似文献
11.
E. -J. Gao L. -L. Jiang D. Zhang W. Jiao T. -L. Liu Y. -J. Zhang G. -L. Wu J. Xu 《Journal of Structural Chemistry》2013,54(5):978-982
A novel coordination polymer constructed with [Co(3,3′-bpbc)(H2O)3]·H2O(I) (3,3′-bpbc = 2,2′-bipyridine-3,3′-dicarboxylic acid) is successfully synthesized at room temperature and characterized by elemental analysis and IR spectra. The crystal structure of the complex is determined by single crystal X-ray diffraction. The unit cell parameters for complex I are: a = 9.9606(11) Å, b = 9.2552(10) Å, c = 16.0258(17) Å, β = 96.731(0)°, V = 1467.2(3) Å3, Z = 4, space group P2(1)/n. In the crystal, the cobalt(II) ion adopts a hexa-coordinate environment, and the structure units aggregate together to give birth to infinite 1D chains. The 2D and 3D framework is constructed via intermolecular hydrogen bonds. 相似文献
12.
用紧束缚 (EHT)晶体轨道方法对层状金属配位聚合物 [{HgX2 (bipy) }n](X =Cl,Br ;bipy =4 ,4′ bipyridyl)进行了能带结构计算 ,并利用键向量方法对这一系列聚合物能带特征和成键性质进行了讨论。研究表明 ,Fermi能级附近的能带主要是金属汞原子和卤素原子及氮原子之间形成的d pσ 反键和d pσ成键作用 ,这两者作用的强弱对导电性起决定作用。本文还对系列聚合物 [{HgX2 (bipy) }n](M =Ni,Cu ,Hg ;X =Cl,Br;bipy =4 ,4′ bipyridyl)可能具有的导电机理和规律进行了探讨。 相似文献
13.
在合成[Co(bpma)(tn)Cl]2+体系配合物的实验中,得到[Co(ptma)(amp)Cl]2+体系的一反式(ptma中仲胺上的氢相对于Cl)经式异构体(m3[ZnCl4]@0.5H2O),其中bpma=N,N′-二(2-吡啶基甲基)胺,tn=1,3丙二胺,ptma=N-(2-吡啶基甲基)丙二胺,amp=2-(氨基甲基)吡啶.此配合物异构体构型选择性形成的原因可能主要是其结构中配体间C-H…π相互作用使之更稳定的结果.利用单晶X-射线衍射法测定的晶体学参数:单斜晶系,空间群C2/c,a=1.55978(19)nm,b=1.33324(16)nm,c=2.2077(3)nm,β=94.832(3)°,V=4.5748(10)nm3,Dc=1.696g@cm-3,Z=8,F000=2360,μ(MoKa)=23.72cm-1,R=0.0475,Rw=0.1204.配合物离子中Co3+为六配位.晶胞中含8个配合物阳离子,8个[ZnCl4]2-阴离子及4个水分子,对映体的比例为1:1. 相似文献
14.
Gabino A. Carriedo F. J. García Alonso S. López Vizcaíno Carlos Díaz Valenzuela Nicolás Yutronic 《Phosphorus, sulfur, and silicon and the related elements》2013,188(7):1549-1558
The reactions of the spirocyclic phosphazene [N 3 P 3 (O 2 C 12 H 8 ) 2 Cl 2 ] (O 2 C 12 H 8 = 2,2'-dioxybiphenyl) with the thiophenols HS--C 6 H 4 --R and M 2 CO 3 (M = K or Cs) in refluxing acetone gave respectively the spirocyclic substituted derivatives [N 3 P 3 (O 2 C 12 H 8 ) 2 (SC 6 H 4 --R) 2 ] R = H ( 2a ), Br ( 2b ), OMe ( 2c ), NO 2 ( 2d ). The reaction is a two-step process the second of which is much faster than the first and the monosubstituted intermediate [N 3 P 3 (O 2 C 12 H 8 ) 2 (SC 6 H 4 --R)Cl] cannot be detected. By contrast, in the analogous reactions with the phenols HO--C 6 H 4 --R and M 2 CO 3 (M = K or Cs) in acetone or THF, to give the known derivatives [N 3 P 3 (O 2 C 12 H 8 ) 2 (OC 6 H 4 --R) 2 ], the first step is faster although both are very dependent on R, M and the solvent. Thus, in the case of the phenol HO--C 6 H 4 --OMe the reaction conditions could be adjusted to give the useful synthetic intermediate monosubstituted derivative [N 3 P 3 (O 2 C 12 H 8 ) 2 (OC 6 H 4 --OMe)Cl] ( 3 ). The reaction of [N 3 P 3 (O 2 C 12 H 8 ) 2 Cl 2 ] with the bifunctional reagent mercaptophenol HS--C 6 H 4 --OH was not specific and led to mixtures of cyclic and oligomeric products. 相似文献
15.
E. J. Gao Z. Wen M. C. Zhu Y. Wang F. C. Liu L. Wang M. Su Y. X. Zhang T. D. Sun S. H. Liu X. N. Gao Y. Zhang 《Russian Journal of Coordination Chemistry》2010,36(10):746-750
In the complex [Cd2(Bipy)2(L)2(H2O)2] · 9H2O, the center atom Cd(II) presents a seven-coordinated pentagonal bipyramidal geometry with seven coordination bonds, four Cd-N bonds, and three Cd-O bonds. X-ray structural analysis shows that nineteen water molecules formed a large water cluster, the cluster and the composition connected to form 2D plane areolar framework and 3D zigzag networks structure through π-π-stacking and hydrogen bonding. This composition in the previous report is rare. 相似文献
16.
Mozhgan Khorasani-Motlagh Meissam Noroozifar Sohaila Mirkazehi-Rigi 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2010,75(2):598-603
The interaction of [Nd(bpy)2Cl3·OH2], where bipy is 2,2′-bipyridine, with DNA has been studied by absorption, emission, and viscosity measurements. [Nd(bpy)2Cl3·OH2] showed absorption decreasing in charge transfer band with increasing of DNA. The binding constant, Kb has been determined by absorption measurement and found to be (1.5 ± 0.1) × 105 M?1. The fluorescent of [Nd(bpy)2Cl3·OH2] has been investigated in detail. The interaction was also studied by fluorescence quenching technique. The results of fluorescence titration revealed that DNA had the strong ability to quenching the intrinsic fluorescence of Nd(III) complex at 327 nm. The binding site number n, apparent binding constant Kb and the Stern–Volmer quenching constant KSV have been determined. Thermodynamic parameters have been calculated according to relevant fluorescent data and Van’t Hoff equation. Characterization of bonding mode has been studied. The results suggested that the major interaction mode between [Nd(bpy)2Cl3·OH2] and DNA was groove binding. 相似文献
17.
[Co(2,3-tir)(amp)Cl]ZnCl4体系中三个几何经式异构体的 识别 总被引:2,自引:0,他引:2
对[Co(2,3-tir)(amp)Cl]ZnCl42,3-tri=N-(2-aminoethyl)-1,3-propanediamine;amp=2-(aminomethyl)pyridine)体系进行了合成,分离出四个配合物。用单晶X射线衍射分析了两个结构,用二维核磁共振DQCOSY和NOESY技术联合解板了另一结构。结构解析显示它们为该体系的四个几何经式异构体(meridianisomers)。两个晶体结构都属中心对称的空间群,表明它们都是外消旋的对映体。 相似文献
18.
对[Co(2,3 -tri) (amp) Cl] ZnCl42, 3 - tri= N - (2 - aminoethyl) - 1,3 - propanediamine; amp = 2 - (aminomethyl)pyridine)体系进行了合成,分离出四个配合物.用单晶X射线衍射分析了两个结构,用二维核磁共振DQCOSY和NOESY技术联合解析了另一结构.结构解析显示它们为该体系的四个几何经式异构体(meridian isomers).两个晶体结构都属中心对称的空间群,表明它们都是外消旋的对映体. 相似文献
19.
对[Co(2,3-tir)(amp)Cl]ZnCl42,3-tri=N-(2-aminoethyl)-1,3-propanediamine;amp=2-(aminomethyl)pyridine)体系进行了合成,分离出四个配合物。用单晶X射线衍射分析了两个结构,用二维核磁共振DQCOSY和NOESY技术联合解板了另一结构。结构解析显示它们为该体系的四个几何经式异构体(meridianisomers)。两个晶体结构都属中心对称的空间群,表明它们都是外消旋的对映体。 相似文献