共查询到20条相似文献,搜索用时 15 毫秒
1.
Four aromatic amines 1-amino-4-phenoxybenzene (A1), 4-(4-aminophenyloxy) biphenyl (A2), 1-(4-aminophenoxy) naphthalene (A3) and 2-(4-aminophenoxy) naphthalene (A4) were synthesized and characterized by elemental, spectroscopic (FTIR, NMR), mass spectrometric and single crystal X-ray diffraction methods. The compounds crystallized in monoclinic crystal system with space group P21. Intermolecular hydrogen bonds were observed between the amine group and amine/ether acceptors of neighboring molecules. Electrochemical investigations were done using cyclic voltammetry (CV), square wave voltammetry (SWV) and differential pulse voltammetry (DPV). CV studies showed that oxidation of aromatic amines takes place at about 0.9 V (vs. Ag/AgCl) and the electron transfer (ET) process has irreversible nature. After first scan reactive intermediate were generated electrochemically and some other cathodic and anodic peaks also appeared in the succeeding scans. DPV study revealed that ET process is accompanied by one electron. DNA binding study of aromatic amines was performed by CV and UV–visible spectroscopy. These investigations revealed groove binding mode of interaction of aromatic amines with DNA. 相似文献
2.
Fabiola Estudiante-Negrete Simón Hernández-Ortega David Morales-Morales 《Inorganica chimica acta》2007,360(5):1651-1660
The organometallic tin(IV) complexes [SnPh2(SRF)2] SRF = −SC6F4-4-H (1), −SC6F5 (2), were synthesized and their reactivity with [MCl2(PPh3)2] M = Ni, Pd and Pt explored. Thus, transmetallation products were obtained affording polymeric [Ni(SRF)(μ-SRF)]n, monomeric cis-[Pt(PPh3)2(SC6F4-4-H)2] (3) and cis-[Pt(PPh3)2(SC6F5)2] (4) and dimeric species [Pd(PPh3)(SC6F4-4-H)(μ-SC6F4-4-H)]2 (5) and [Pd(PPh3)(SC6F5)(μ-SC6F5)]2 (6) for Ni, Pt and Pd, respectively. The crystal structures of complexes 1, 2, 3, 4 and 6 were determined. 相似文献
3.
D CourtneyN.L Cromhout D CunninghamJ.F Gallagher A.R Manning P McArdleS.I Pratt 《Inorganica chimica acta》2002,327(1):98-107
The iron hydrido complex HFe(CO)2{P(OPh)3}{(PhO)2POC6H4} (1), was rapidly deprotonated by DBU or [BzMe3N][OH] in THF to afford the new carbonyl iron anion [Fe(CO)2{P(OPh)3}{(PhO)2POC6H4}]− ([2]−), containing an ortho-metallated triphenyl phosphite ligand. Complex [2]− reacted with triorganostannyl and plumbyl salts and with halogens to give the octahedral FeII compounds Fe(CO)2{P(OPh)3}{(PhO)2POC6H4}(X) (X=SnPh3, 3; SnMe3, 4; PbPh3, 5; PbMe3, 6; Cl, 7; Br, 8; I, 9). The Group 14 complexes 3-6 were obtained in one isomeric form in which the PIII-donor atoms are mutually cis, the carbonyl ligands are cis and the P(OPh)3 and MR3 (M=Sn, Pb; R=Ph, Me) groups are trans as determined by solution-state IR, 31P and 13C NMR spectroscopic data. This geometry was confirmed for 3 by a single crystal X-ray diffraction study. The halide complexes, however, were obtained as a mixture of isomers. The major isomer (7, X=Cl; 8a, X=Br; 9a, X=I) has cis P atoms, trans CO groups and the halide located trans to the phosphorus atom of the ortho-metallated phosphite ligand. The structure of 9a was confirmed by an X-ray diffraction study. Two other isomers, designated 8b (X=Br) and 9b (X=I), with cis P atoms and cis CO groups were isolated from the reactions of [2]− with Br2 and I2, respectively. The structure of the latter was established by X-ray crystallography and is related to 9a by exchange of the P(OPh)3 ligand and a carbonyl group such that the metal-bound C atom of the five-membered metallacycle is trans to CO. The stereo-geometry of 8b could not be unambiguously assigned from the spectroscopic data; however, two of the seven possible geometric isomers were suggested as plausible structures. 相似文献
4.
(meta-Cyanophenyl) rhodium porphyrins have been synthesized from the selective activation of a meta carbon-hydrogen bond of PhCN via the reaction of RhCl3 with porphyrins in refluxing PhCN. 相似文献
5.
Dietrich P. Steinhuebel Peter Fuhrmann Stephen J. Lippard 《Inorganica chimica acta》1998,270(1-2):527-536
A series of zirconium(IV) complexes, [ZrX2(XDK)], where XDK is the constrained carboxylate ligand m-xylylenediamine bis(Kemp's triacid imide), were prepared and structurally characterized. The solid state structure of the mononuclear carboxylate alkyl complex [Zr(CH2Ph)2(XDK)] reveals that one benzyl group is bonded in an η2-fashion to the metal center. The reactivity of [Zr(CH2Ph)2(XDK)] displays its electrophilic character toward nucleophiles strong enough to displace the η2-benzyl group. Thus, weak sigma donor ligands such as CO, alkynes and anilines do not react, whereas strong sigma donors, such as pyridines and isocyanides, rapidly form the monoadduct [Zr(CH2Ph)2(4-tert-butylpyridine)(XDK)] and [Zr{η2-2,6-Me2PhNCCH2Ph}2(XDK)], an η2-iminoacyl derivative, respectively. Attempts to prepare zirconium amido complexes with H2XDK generally afforded the eight-coordinate [Zr(XDK)2] complex but use of the small amido ligand precursorZr(NMe2)4 allowed [Zr(NMe2)2(4-tert-butylpyridine)(XDK)] to be isolated in good yield. 相似文献
6.
New water-soluble rhodium(III) complexes with a tacn (1,4,7-triazacyclononane) and a bpy (2,2′-bipyridine) supporting ligands were synthesized. The reaction of [RhIII(tacn)Cl3] (1) with equimolar amount of bpy and two equivalents of AgNO3 in H2O at reflux for 10 h gave a water-soluble chloro complex [RhIII(tacn)(bpy)Cl](NO3)2 {2(NO3)2}. Complex 2(NO3)2 was treated with equimolar amount of AgNO3 in H2O at reflux for 10 h to give a water-soluble nitrato complex [RhIII(tacn)(bpy)(NO3)](NO3)2 {3(NO3)2}. Water-solubility of 3 with NO3 − ligand (46.5 mg/mL) is high compared with that of 2 with Cl− ligand (14.5 mg/mL) under the same conditions (at pH 7.0 at 25 °C). The structures of 2 and 3 were unequivocally determined by X-ray analysis. Their structures in H2O were also examined by 1H NMR, IR, and electrospray ionization mass spectrometry (ESI-MS). 相似文献
7.
Bangbo Yan 《Inorganica chimica acta》2006,359(1):118-126
Three new one-dimensional copper coordination polymers have been prepared and fully characterized by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and magnetic susceptibility measurements. The structure of [Cu(CN)2(bpy)] (1) (bpy = 2,2-bipyridyl) (monoclinic P21/c, a = 8.9761(7) Å, b = 16.731(1) Å, c = 8.0224(6) Å, β = 114.437(1)°) consists of Cu(II) metal centers coordinated by three cyanide ligands and chelated by one bpy to form the monomers Cu(CN)3(bpy) with distorted square pyramidal geometry. Each monomer shares two cyanide ligands with two adjacent monomers to form infinite -Cu(II)-CN-Cu(II)-CN-Cu zigzag chains along the c-axis. The one-dimensional structure of [Cu(CN)(bpy)] (2) (hexagonal P32, a = 14.4883(6) Å, b = 12.921(1) Å) is built of tetrahedral Cu(CN)2bpy metal complexes in which Cu(I) metal centers are coordinated by one nitrogen and one carbon from two different CN ligands, and two nitrogens from one bpy. The two CN ligands act as bridging ligands between adjacent monomers to form helical chains along the 32 screw axis. The crystal structure of [Cu2Cl(CN)(bpy)] (3) (orthorhombic Pbca, a = 17.853(2) Å, b = 6.9724 (9) Å, c = 18.7357 (9) Å) consists of two monomers, CuCl2(CN) and Cu(bpy)(CN) that share a cyanide ligand to form Cu2Cl2(CN)(bpy) dimers. The dimers link to each other by sharing Cl ligands leading to the formation of infinite Cu-Cl-Cu chain decorated by the complex Cu(CN)(bpy). Variable-temperature magnetic measurement shows an overall ferromagnetic behavior for compound 1. The magnetic pathway of compound 1 is through the cyanide bridge connecting apical and equatorial positions of adjacent copper (II) ions. 相似文献
8.
P. Bouziotis D. Papagiannopoulou I. Pirmettis M. Pelecanou C. P. Raptopoulou C. I. Stassinopoulou A. Terzis M. Friebe H. Spies M. Papadopoulos E. Chiotellis 《Inorganica chimica acta》2001,320(1-2):174-177
Two novel five-coordinate cis-dioxorhenium(V) complexes of the general formula ReO2[R2NCH2CH2S][PPh3] (R2N=Et2N, complex 1 and R2N=(o-CH3O---C6H4N(CH2CH2)2N, complex 2) have been synthesized by reacting ReOCl3(PPh3)2 with the respective bidentate ligands R2NCH2CH2SH. The complexes have been characterized by elemental analysis, IR, NMR spectroscopies and X-ray crystallography. X-ray crystallographic studies showed that the coordination geometry around rhenium is distorted trigonal bipyramidal. The basal plane is defined by the two doubly bonded oxygen atoms and the sulfur of the bidentate ligand, while the nitrogen of the ligand and the phosphorus occupy the apical positions. 相似文献
9.
N. Kositzyna M. Antipin K. Lyssenko P. S. Pregosin G. Trabesinger 《Inorganica chimica acta》1996,250(1-2):365-373
A series of cationic allyl complexes of Pd(II) derived from the diterpene carvone
have been synthesised and characterised using the chelating ligands, bipyridine, 1,8-phenanthroline, neocuproin, S,S (-)-Chiraphos and R (+)-Binap as co-ligands. These complexes can be readily converted to new organic products in which one C---H bond of the allyl methyl has been substituted. The structure of a bipyridyl complex as its tetraphenyl borate salt has been determined via X-ray diffraction. 2-D NOESY studies on the Chiraphos and Binap complexes are reported. The Binap, but not the Chiraphos, complex reveals η3-η3η3 isomerisation at ambient temperature. 相似文献
10.
The complex [Ru(SB12H11)(NH3)5]·2H2O has been prepared by the reaction of Cs2B12H11SH with [RuCl(NH3)5]Cl2 in aqueous solution. The complex represents the first reported example of the borocaptate anion acting as a ligand. The structure of the complex has been determined by single crystal X-ray diffraction analysis. The crystal parameters are monoclinic, space group P21/c, A = 8.056(1), B = 14.240(2), C = 15.172(2) Å, β=98.48° and Z = 4. The ruthenium atom has a distorted octahedral coordination. The distortion is probably due to the high (3−) charge and the large bulk of the borocaptate ligand. These features can also be observed in the spectroscopic properties of the complex. 相似文献
11.
Attempted syntheses of ruthenium(II) monosubstituted squarate complexes in acetonitrile using cis-[RuCl2(dmso)4] and anisole-, methoxy-, methyl- and diphenylamino-squarate ligands, respectively, resulted in the formation in each case of the monomer cis, fac-Ru(CH3CN)Cl2(dmso)3 (1) with the ruthenium atom in a distorted octahedral environment. A second crop of crystals harvested from the reaction with the methoxysquarate ligand was identified as the oxalato-bridged dimer [{cis-(CH3CN)(Cl)(dmso)2Ru}2(μ-C2O4)] (2). When cis-[RuCl2(dmso)4] and methylsquarate were reacted in aqueous solution instead of acetonitrile, the dimer [{fac-(Cl)(dmso)3Ru}2(μ-C2O4)] (3) was produced. The dimers 2 and 3 are formed from oxidation/ring opening of the methoxy- and methyl-squarate ligands, respectively. Use of the salts of these ligands instead of their non-ionised forms under different reaction conditions, afforded [Na] fac-[RuCl3(dmso)3] (4) and [(C4H9)4N]2[(C4O4)(C4H2O4)2] (7), respectively, which were shown to be products of competing reactions. The information acquired from these failed attempts has provided the basis for the development of a strategy to overcome these problems and lead to a successful synthetic route to ruthenium(II) monosubstituted squarates. 相似文献
12.
Hirotaka Nagao Dai Ooyama Toshiyuki Hirano Hiroshi Naoi Megumi Shimada Sachiko Sasaki Noriharu Nagao Masao Mukaida Takao Oi 《Inorganica chimica acta》2001,320(1-2):60-66
Isocyanato and isothiocyanatopolypyridineruthenium complexes, [Ru(NCX)Y(bpy)(py)2]n+ (bpy=2,2′-bipyridine, PY=pyridine; X=O, Y=NO2 for n=0, and Y=py for n=1; X=S, Y=NO2 for n=0, Y=NO for n=2, and Y=py for n=1), were synthesized by the reaction of polypyridineruthenium complexes with potassium cyanate or sodium thiocyanate salt. Isocyanatoruthenium(II) complexes, [Ru(NCO)(NO2)(bpy)(py)2] and [Ru(NCO)(bpy)(py)3]+, react under acidic conditions to form the corresponding ammineruthenium complexes, [Ru(NO)(NH3)(bpy)(py)2]3+. The molecular structures of [Ru(NCO)(bpy)(py)3]ClO4, [Ru(NCS)(NO)(bpy)(py)2](PF6)2 and [Ru(NO)(NH3)(bpy)(py)2](PF6)3 were determined by X-ray crystallography. 相似文献
13.
The nickel arsenatotungstate K10[As2W19(H2O){Ni(H2O)}2O67]·18H2O (1) has been synthesized. Due to its instability in water, attempts to obtain crystals of 1 suitable for X-ray diffraction have failed. The stabilization of the [As2W19(H2O){Ni(H2O)}2O67]10− core has been reached by synthesizing the analogue mixed {CsK} salt. The crystal structure of Cs6K2[Ni(H2O)6][As2W19(H2O){Ni(H2O)}2O67]·17H2O (2) has been resolved. It consists of two [α-AsW9O33]9− sub-units linked via a belt containing a tungsten and two nickel cations. Comparison of infrared and electronic absorption spectroscopic data for 1 and 2 has confirmed the structure proposed for 1. The instability of 1 led us to investigate the behavior of 1 in water. UV-Vis spectroscopy revealed that the formation of this complex is a multi-step reaction. An intermediate, the complex K8[Ni(H2O)6]1.5[As2W19(H2O){K(H2O)}{Ni(H2O)4}O67]·21H2O (3), has been isolated and characterized by elemental analysis, UV-Vis and infrared spectroscopies, and X-ray diffraction. In 3, the two vacant sites of the [As2W19O67]14− anion are occupied by a nickel and a potassium, forming a {WNiK} belt. It follows that the stability of 2 in water is due to the large ionic radius of Cs+, which prevents the inclusion of the alkaline cation into the cavity of the [As2W19O67]14− anion. The complex 3 represents a unique example of a fully characterized intermediate leading to the formation of a sandwich-type polyoxometalate. 相似文献
14.
Three mono- and dinuclear nickel complexes with dichalcogenolate o-carboranyl ligands were synthesized and characterized by X-ray crystallography. The reactions of Ni(COD)2(COD=1,5-octadiene) with [(THF)3LiE2C2B10H10Li(THF)]2 (E=S, Se) in THF in the presence of air in different ratios afforded the mono- and dinuclear nickel complexes of formulae Li(THF)4]2[Ni(E2C2B10H10)2] (E=S, 1a; E=Se, 1b) and [Li(THF)4]2[Ni2(E2C2B10H10)3] (E=S, 2a; E=Se, 2b). In 2a, two nickel atoms are connected by one chalcogen (η1,η2-S2C2B10H10) bridging ligand with strong metal-metal interaction. Complex of formula (PPh3)2Ni(S2C2B10H10) · 0.5THF (3a) was also obtained from the reaction of (PPh3)2NiCl2 and [(THF)3LiS2C2B10H10Li(THF)]2. 相似文献
15.
16.
Jürgen Zeller 《Inorganica chimica acta》2004,357(6):1813-1821
The paper describes the reactivity of calix[4]arene dialkyl- or -silylethers H2R2calix, R=Me (1), Bz (2), or SiMe3 (3) (p-tert.butyl-calix[4]arene=H4calix), towards the iron(III) complex [FeCl(NSiMe3)2(thf)] 4. Bis(silylation) of H4calix was achieved using a mixture of NEt3 and Me3SiCl as silylating agent, which is probably the most convenient and cheapest way for the preparation of H2(Me3Si)2calix 3. [FeCl(N{SiMe3}2)2(thf)] 4 has been obtained from the reaction of [FeCl3] and commercially available K[N(SiMe3)2] in THF. The reactions of 4 with H2Me2calix and H2Bz2calix afford mononuclear iron(III) chloro compounds [FeCl(R2calix)] 5 (R=Me) and 6 (R=Bz). The usage of calix[4]arene silyl ether 3 leads to a dinuclear complex [Fe2({Me3Si}calix)2] 7, presumably under Me3SiCl cleavage of a mononuclear calixarene iron(III) chloro complex. The calix[4]arene ether stabilized iron(III) chloro complexes are susceptible to nucleophilic substitution reactions, as exemplified by the reaction of 5 with sodium azide yielding an azido complex [Fe(N3)(Me2calix)] 8. The molecular structures of 4, 5, 6, 7, and 8 in the solid state have been determined by X-ray diffraction. 相似文献
17.
Four 2-acetylpyridine 4N-alkyl thiosemicarbazones, and their Ga(III) and In(III) complexes have been prepared and characterised by fluorescence, UV-Vis, IR, 1H and 13C NMR spectroscopy, mass spectrometry and X-ray crystallographic analysis. Comparison of the crystal structures gave an insight into the nature of the complexes formed, demonstrating a preference for [ML2]+ type complexes with gallium and [MLX3] species with indium. Stability studies on two candidates indicated that complex [InL3Cl2MeOH] was stable to chemical degradation for prolonged periods in human serum, giving this complex potential for further biological evaluation. 相似文献
18.
Reaction of the ligands 3-phenyl-5-(2-pyridyl)pyrazole (HL1), 3,5-bis(2-pyridyl)pyrazole (HL2), 3-methyl-5-(2-pyridyl)pyrazole (HL3) and 3-methyl-5-phenylpyrazole (HL4) with [MCl2(CH3CN)2] (M = Pd(II), Pt(II)) or [PdCl2(cod)] gives complexes with stoichiometry [PdCl2(HL)2] (HL = HL1, HL2, HL3), [Pt(L)2] (L = L1, L2, L3) and [MCl2(HL4)2] (M = Pd(II), Pt(II)). The new complexes were characterised by elemental analyses, conductivity measurements, infrared and 1H NMR spectroscopies. The crystal and molecular structure of [PdCl2(HL1)] was resolved by X-ray diffraction, and consists of monomeric cis-[PdCl2(HL1)] molecules. The palladium centre has a typical square planar geometry, with a slight tetrahedral distortion. The tetra-coordinated metal atom is bonded to one pyridine nitrogen, one pyrazolic nitrogen and two chloro ligands in a cis disposition. The ligand HL1 is not completely planar. 相似文献
19.
Guibin Ma Andrey Ilyukhin Julius Glaser Imre Tth Lszl Zkny 《Inorganica chimica acta》2001,320(1-2):92-100
The formation of three [Tl(en)n]3+ complexes (n=1–3) in a pyridine solvent has been established by means of 205Tl and 1H NMR. Their stepwise stability constants based on concentrations, Kn=[Tl(en)n 3+]/{[Tl(en)n−1 3+]·[en]}, at 298 K in 0.5 M NaClO4 ionic medium in pyridine, were calculated from 205Tl NMR integrals: log K1=7.6±0.7; log K2=5.2±0.5 and log K3=2.64±0.05. Linear correlation between both the 205Tl NMR shifts and spin–spin coupling 205Tl–1H versus the stability constants has been found and discussed. A single crystal with the composition [Tl(en)3](ClO4)3 was synthesized and its structure determined by X-ray diffraction. The Tl3+ ion is coordinated by three ethylenediamine ligands via six N-donor atoms in a distorted octahedral fashion. 相似文献
20.
Donald J. Darensbourg Kevin K. Klausmeyer Jennifer D. Draper Jennifer A. Chojnacki Joseph H. Reibenspies 《Inorganica chimica acta》1998,270(1-2):405-413
The complex [Et4N][W(CO)5OMe] (1) has been prepared from the reaction of the photochemically generated W(CO)5THF adduct and [Et4N][OH] in methanol. Complex 1 was shown to undergo rapid CO dissociation in THF to quantitatively provide the dimeric dianion, [W(CO)4OMe]22−. The resulting THF insoluble salt [Et4N]2[W(CO)4OMe]2 (2) has been structurally characterized by X-ray crystallography, with the doubly bridging methoxide ligands being in an anti configuration. Complex 2 was found to subsequently react with excess methoxide ligand in a THF slurry to afford the face-sharing octahedron complex [Et4N]3[W2(CO)6(OMe)3] (3) which contains three doubly bridging methoxide groups. In the absence of excess methoxide ligand complex 2 cleanly yields the tetrameric complex [Et4N]4[W(CO)3OMe]4 (4) which has been structurally characterized as a cubane-like arrangement with triply bridging μ3-methoxide groups and W(CO)3 units. Although complex 3 was not characterized in the solid state, the closely related glycolate derivative [Et4N]3[W2(CO)6(OCH2CH2OH)3] (5) was synthesized and its structure determined by X-ray crystallography. The trianions of complex 5 are linked in the crystal lattice by strong intermolecular hydrogen bonds. Crystal data for 2: space group P21/n, a = 7.696(2), b = 22.019(4), c = 9.714(2) Å, β = 92.22(3)°, Z = 4, R = 6.43%. Crystal data for 4: space group Fddd, a = 12.433(9), b = 24.01(2), c = 39.29(3) Å, Z = 8, R = 8.13%. Crystal data for 5: space group P212121, a = 11.43(2), b = 12.91(1), c = 29.85(6) Å, Z = 8, R = 8.29%. Finally, the rate of CO ligand dissociation in the closely related aryloxide derivatives [Et4N][W(CO)5OR] (R = C6H5 and 3,5-F2C6H3) were measured to be 2.15 × 10−2 and 1.31 × 10−3 s−1, respectively, in THF solution at 5°C. Hence, the value of the rate constant of 2.15 × 10−2 s−1 establishes a lower limit for the first-order rate constant for CO loss in the W(CO)5OMe− anion, since the methoxide ligand is a better π-donating group than phenoxide. 相似文献