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1.
《Journal of Coordination Chemistry》2012,65(4):187-207
Abstract The crystal structures of several crown ether and polyethylene glycol complexes of HgX2 (X=Cl, Br, I) have been investigated. The crown ether complexes studied are [HgX2(18-crown-6)] (X=Br, I) and [HgI2(dibenzo-18-crown-6)]·CH3CN. In each case Hg resides in the cavity of the ether resulting in hexagonal bipyramidal geometry with axial, terminal halides. The covalently bonded halides reside closer to Hg than the oxygen donor atoms. Five polyethylene glycol complexes have been structurally characterized: [(HgCl2)3(EO3)], [HgX2(EO4)] (X=Br, I), [HgCl2(EO5)], and [HgBr2(EO5)HgBr2]2 (EO3=triethylene glycol, EO4=tetraethylene glycol, EO5=pentaethylene glycol). The EO4 and EO5 glycols mimic crown ethers by forming an equatorial girdle around Hg although in each case one alcoholic terminal end does not coordinate to the metal ion. Each complex also has two covalent, nearly linear, axial halides coordinated to Hg. In [(HgCl2)3(EO3)], the glycol is linear and coordinates to three Hg atoms all on the same side of the glycol ligand. This structure is polymeric via chloride bridging. 相似文献
2.
Monica Toma Agustín Sánchez María S. García-Tasende José S. Casas José Sordo Eduardo E. Castellano Javier Ellena 《Central European Journal of Chemistry》2004,2(3):534-552
Synthesis, spectral properties and crystal structure of dimethylthallium(III) complexes with 2-mercaptonicotinic acid (2mna),
2-mercapto-methyl-nicotinate (2mmn), 2-mercapto-ethyl-nicotinate (2men) and 2-mercapto-isopropyl-nicotinate (2min) are reported.
The compounds were characterized using IR, multinuclear NMR (1H,13C,205Tl) and mass spectrometry (electrospray, ES-API). The molecular structures of [TlMe2(2mna)]·H2O, (1), [TlMe2(2mmn)], (2), [TlMe2(2men)], (3) and [TlMe2(2min)], (4) were determined by the single-crystal X-ray diffraction. In 1, the monodeprotonate O,S-bidentate ligand chelates one dimethylthallium
(III) unit and simultaneously bridges (O and S) between two of these organometallic units. The Tl-O1′ and Tl-S″ interactions
are leading to polymeric chain linked in a three-dimensional network by the hydrogen bonds formed between the water molecule
and the oxygen O (2) atom of the acid. The thallium atom is in a distorted octahedral environment with a [TlC2O2S2] kernel. Compounds 2, 3 and 4 are similar, in all the cases already mentioned the ligand is NH deprotonated and is strongly coordinated to two dimethylthallium
(III) units through the N and S atoms. Two additional weak interactions with the O and S atoms lead to a [TlC2NOS2] kernel for the metal atom, in which the coordination polyhedron is a very distorted octahedron with the methyl groups occupying
the apical positions. 相似文献
3.
《Journal of Coordination Chemistry》2012,65(1-2):97-108
Abstract The synthesis of the new ligand 1,8-bis(quinolyloxy)-3,6-dithiaoctane (1) and the corresponding Cu(II), Cu(I) and Co(II) complexes is reported. The crystal and molecular structure of the copper(II) complex, [Cu(1)](ClO4)2.3H2O, has been determined by X-ray diffraction methods. The complex crystallizes in the orthorhombic space group Fddd, with cell data Z = 16, a = 20.326(2), b = 20.879(3) and c = 28.308(4)Å. The structure consists of discrete [Cu(1)]?2+ cations separated by (structurally disordered) perchlorate anions and three lattice water molecules per cation. The coordination geometry about the copper atom is pseudo-octahedral with the quinoline nitrogen and thioether sulfur atoms at the equatorial positions and the ether oxygen atoms at the axial positions. 1H NMR line-broadening experiments indicate that electron-transfer self-exchange reactions between the copper(I) and copper(II) complexes of (1) is immeasurably slow on the NMR time-scale. The coordination chemistry of (1) is compared with its oxygen analogue, 1,8-bis(quinolyloxy)-3,6-dioxaoctane. 相似文献
4.
Jos. S. Casas Eduardo E. Castellano Javier Ellena María S. García‐Tasende Agustín Snchez Jos Sordo Ezequiel M. Vzquez‐Lpez María J. Vidarte 《无机化学与普通化学杂志》2003,629(2):261-267
The reaction of 2, 6‐diacetylpyridine bis(thiosemicarbazone) (H2DAPTSC) with dimethylthallium hydroxide yielded the complexes [(TlMe2)2(DAPTSC)] and [TlMe2(HDAPTSC)]. The structure of [TlMe2(HDAPTSC)], determined by X‐ray diffractometry, exhibits a hitherto unknown coordination mode of the HDAPTSC— anion in which its deprotonated thiosemicarbazone chain coordinates one metal atom through its sulphur and hydrazinic N atoms while a second metal atom is weakly coordinated through the S atom of the undeprotonated thiosemicarbazone chain. Each thallium atom is coordinated in both ways, with the result that the [TlMe2(HDAPTSC)] units are linked in infinite helical chains in the direction of the b axis. When reacting with diphenylthallium(III) hydroxide, H2DAPTSC induced a dephenylation process which led to the monophenylthallium(III) complex [TlPh(DAPTSC)]. Recrystallization from acetone yielded crystals of [TlPh(DAPTSC)]·C3H6O in which X‐ray diffractometry showed DAPTSC2— to be pentadentate, coordinating through its sulphur, azomethine N and pyridine N atoms. The 1H, 13C and 205Tl NMR data of [TlPh(DAPTSC)] indicate that its solid state molecular structure persists in DMSO solution, while those of [TlMe2(HDAPTSC)] indicate rapid alternation between coordination of the metal atom to one of the HDAPTSC— thiosemicarbazone chains and its coordination to the other. 相似文献
5.
《Journal of Coordination Chemistry》2012,65(3):269-279
Abstract Two new cadmium(II) complexes with phenylthiourea (PTU), namely Cd(PTU)4Cl2 (1) and [Cd2(NCS)2(μ2-SCN)2(PTU)2(μ2-PTU)2] n (2), have been prepared and characterized structurally by X-ray diffaction. Complex 1 crystallizes in the monoclinic space group C2/c, with a = 27.057(13), b = 8.108(3), c = 16.751(8) Å, β = 114.46°, V = 3345(3) Å3, Z = 4. Complex 2 crystallizes in the triclinic space group P-1, with a = 9.336(3), b = 14.686(5), c = 16.911(5) Å, α = 71.36(2), β = 84.31(2), γ = 72.470(10)°, V = 2095.0(12) Å3 Z = 4. The structural analysis shows that each metal atom in both the mononuclear complex 1 and polynuclear complex 2 is octahedrally coordinated by four sulfur atoms and two chloro ligands or two nitrogen atoms from the thiocyanate groups, respectively. The PTU ligand can serve as either a monodentate ligand or a μ2-bridging ligand upon coordination to a metal atom. 相似文献
6.
《Journal of Coordination Chemistry》2012,65(20):3245-3252
Two new complexes, [Co2(CH2=C(CH3)CO2)4(phen)2(H2O)2] (1) and [Pb2(CH2=C(CH3)CO2)4(phen)2] (phen = 1,10-phenanthroline) (2), have been synthesized and structurally characterized by single crystal X-ray diffraction methods. There are two cocrystallized conformers of [Co(CH2=C(CH3)CO2)2(phen)(H2O)] in the asymmetric unit of 1 with the Co atoms displaying similar coordination modes. In the asymmetric unit of 2, there exist two crystallographically independent [Pb(CH2=C(CH3)CO2)2(phen)] molecules with the Pb atoms showing completely different coordination geometries. Weak intermolecular interactions such as hydrogen bonding and π–π stacking are responsible for the supramolecular assembly and stabilization of the crystal structures of 1 and 2. The complexes are characterized by elemental analysis, IR spectra, and UV–Vis spectra. The fluorescent properties of 2 are also discussed. 相似文献
7.
《Journal of Coordination Chemistry》2012,65(4):593-599
Two new copper(II) complexes, [CuL2] (1) and [Cu2L2(NCS)2] · 2CH3CN (2) (HL = 2-bromo-4-chloro-6-[(2-morpholin-4-ylethylimino)methyl]phenol), have been synthesized and characterized by elemental analyses, infrared spectroscopy, and single-crystal X-ray diffraction. Complex 1 was synthesized by reaction of HL with copper(II) acetate in methanol, while 2 was synthesized by adding ammonium thiocyanate to a methanol/acetonitrile (V : V = 2 : 1) solution of 1. Complex 1 crystallizes in the P21/n space group, and the thiocyanato-bridged dinuclear copper(II) complex, 2, crystallizes in the Pbcn space group. The Cu in 1 is four-coordinate square-planar with two imine N and two phenolate O atoms from two Schiff-base ligands. The Cu in 2 is five-coordinate square-pyramidal with NNO donor atoms of one Schiff-base ligand and one N atom of a bridging thiocyanate ligand defining the basal plane, and with one S atom of another bridging thiocyanate ligand occupying the apical position. 相似文献
8.
《Journal of Coordination Chemistry》2012,65(3-4):303-312
Abstract The coordination properties of 5-amino-1,3,4-thiadiazole-2-sulfonamide (Hats) with Cu(II), Ni(II) and Zn(II) ions, are analyzed. Although the ligand presents several donor atoms, we have only observed three coordination behaviors: (i) as a monodentate ligand through the Nsulfonamido atom, (ii) as a bridging ligand linking the metal ions through the Nsulfonamido and Nthiadizole atoms and (iii) as a bridging ligand linking metal ions through the N and O atoms of the sulfonamidate group. It is noteworthy that coordination mode (iii) is observed for the first time in heterocyclic sulfonamides complexes. In addition, the conformation of the Hats as counter-ion is analyzed and compared with the conformations that the ligand adopts in metal complexes. 相似文献
9.
《Journal of Coordination Chemistry》2012,65(3):183-188
Five new complexes, [M(CO)5(salmsh)] (M?=?Cr;?1,?Mo;?2,?W;?3), [Re(CO)4Br(salmsh)], 4, and [Mn(CO)3 (salmsh)], 5, have been synthesized by the photochemical reaction of metal carbonyls with salicylaldehyde methanesulfonylhydrazone (salmsh). The complexes have been characterized by elemental analyses, EI mass spectrometry, FT-IR and 1H NMR spectroscopy. The spectroscopic studies show that salmsh behaves as a monodentate ligand coordinating via the imine N donor atom in 1–4 and as a tridentate ligand in 5. 相似文献
10.
Four Schiff base complexes, [Zn2L2(NCS)2] ( 1 ), [Cd2L2(NCS)2]n ( 2 ), [Zn4L2(N3)2Cl4(OH2)(CH3OH)] ( 3 ), and [Cu4L2(N3)2Cl4(OH2)(CH3OH)] ( 4 ) (where L = 2‐[(2‐dimethylaminoethylimino)methyl]phenol), were synthesized and characterized by elemental analyses, infrared spectroscopy, and single crystal X‐ray determinations. Both 1 and 2 are structurally similar polynuclear complexes. In 1 , each Zn atom has a slightly distorted square‐pyramidal coordination configuration. In the basal plane, the Zn atom is coordinated by one O and two N atoms of one L, and by one O atom of another L. The apical position is occupied by one terminal N atom of a coordinated thiocyanate anion. The Zn···Zn separation is 3.179(3) Å. While in 2 , the Cd1 atom is six‐coordinated in an octahedral coordination. In the equatorial plane, the Cd1 atom is coordinated by one O and two N atoms of one L, and by one O atom of another L. The axial positions are occupied by the terminal N and S atoms from two bridging thiocyanate anions. The coordination of Cd2 atom in 2 is similar to those of the zinc atoms in 1 . The Cd···Cd separation is 3.425(2) Å. Both 3 and 4 are novel tetra‐nuclear complexes. Each metal atom in the complexes has a slightly distorted square‐pyramidal coordination. The arrangements of the terminal metal atoms are similar, involving one O and two N atoms of one L ligand and one bridging Cl atom defining the basal plane, and one O atom of a coordinated water molecule or MeOH molecule occupying the apical position. The coordinations of the central metal atoms are also similar. The basal plane of each metal atom involves one O atom of one L ligand, one terminal Cl atom, and two terminal N atoms from two bridging azide groups. The apical position is occupied by a bridging Cl atom which also acts as a basal donor atom of the terminal metal atom. The Schiff base ligand and the four complexes showed high selectivity and antibacterial activities against most of the bacteria. 相似文献
11.
Almudena Amoedo‐Portela Rosa Carballo Jos S. Casas Emilia García‐Martínez Ana B. Lago‐Blanco Angeles Snchez‐Gonzlez Jos Sordo Ezequiel M. Vzquez‐Lpez 《无机化学与普通化学杂志》2005,631(11):2241-2246
The new ligand bis(4‐pyridylthio)methane (4‐bpytm) ( 1 ) and its complexes [CuX2(4‐bpytm)] and [CuX2(4‐bpytm)2] (X = Cl and Br) ( 2 – 5 ) have been prepared and characterized by elemental analysis, IR‐Raman, UV/Vis spectroscopy. The structures of (4‐bpytm) ( 1 ), [CuCl2(4‐bpytm)2] ( 3 ) and [CuBr2(4‐bpytm)2] ( 4 ) were determined by single‐crystal X‐ray diffraction analysis. X‐ray analysis of the 1:2 derivatives reveals that the copper atom has a distorted (4 + 2) octahedral environment. The copper atom is coordinated by four nitrogen atoms from four bridging 4‐bpytm ligands and two halogen atoms. The axial Cu–N bonds are considerably longer than the equatorial Cu–N bonds owing to JahñTeller distortion. CuX2 units are linked to each other through bridging 4‐bpytm ligands to form a 2D interpenetrated coordination polymer. The structural parameters of the 4‐bpytm ligand in these complexes were compared with those of the free ligand. 相似文献
12.
《Journal of Coordination Chemistry》2012,65(3-4):205-215
Abstract Nickel(II) complexes with a combination of trithiocyanuric acid and diamines or triamines of composition [Ni(aepa)(ttcH)(H2O)], [Ni(dien)(ttcH)(H2O)], [Ni(dpta)(ttcH)(H2O)] H2O, [Ni(phen)2(ttcH)]H2O, [Ni(phen)3](ttcH)-5H2O and [Ni(1,2-pn)3](ttcH)-H2O (aepa = N-(2-aminoethyl)-1,3-propanediamine,dien = diethylenetriamine,dpta = dipropylenetnamine, phen = 1,10-phenanthroline, 1,2-pn = 1,2-diaminopropane. ttcH3 = trithiocyanuric acid) have been prepared. The compounds have been characterized by means of elemental analysis, IR and electronic spectroscopies and magnetochemical measurements. Selected complexes were studied by thermal analysis. The compounds can be characterized as distorted octahedral Ni(II) complexes. It was found that the trithiocyanuric dianion can act either as a bidentate ligand or be situated out of the coordination sphere of nickel. The crystal and molecular structure of [Ni(dpta)(ttcH)(H2O)] H2O was determined. Crystals are monoclinic, space group P21/n, with a = 20.316(4), b = 7.967(2), c = 21.401(4) Å, β = 99.23(3)°, K=3419.1(13)Å3, Z = 4, T = 293 K. The nickel(II) atom is six-coordinated by three nitrogen atoms from dipropylene-triamine, nitrogen and sulphur from trithiocyanuric acid, and an oxygen atom from a water molecule in a distorted octahedral geometry. 相似文献
13.
《Journal of Coordination Chemistry》2012,65(4):331-339
Abstract Equilibrium constants involving the ternary mixed ligand iron(II) complex [Fe(TPTZ)(terpy)]2+, determined spectrophotometrically at 23° and μ=0.5 M, are reported. Acidity constants of the protonated ligands and formation constants of the binary iron(II) complexes [Fe(TPTZ)2]2+ and [Fe(terpy)2]2+, measured as an adjunct to determining the ternary complex constants, are also reported. The results are of interest in elucidating mixed-ligand complexation effects as well as in confirming or correcting previously reported equilibrium constants of the binary complexes. 相似文献
14.
《Journal of Coordination Chemistry》2012,65(14):1609-1614
Two new uranyl complexes [UO2(DPDPU)2(NO3)2](C6H5CH3) (1) and [UO2(PMBP)2 (DPDPU)](CH3C6H4CH3)0.5 (2), (DPDPU?=?N,N′-dipropyl-N,N′-diphenylurea, HPMBP?= 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5) were synthesized and characterized. The coordination geometry of the uranyl atom in 1 is distorted hexagonal bipyramidal, coordinated by two oxygen atoms of two DPDPU molecules and four oxygen atoms of two bidentate nitrate groups. The coordination geometry of the uranyl atom in 2 is distorted pentagonal bipyramidal, coordinated by one oxygen atom of one DPDPU molecule and four oxygen atoms of two chelating PMBP molecules. 相似文献
15.
C om m ent Sulfasalazine is in a class of m edications called anti-inflam m atory drugs, which is used to treatbowel inflam m ation,diarrhea (stoolfrequency),rectalbleed- ing, and abdom inal pain in patients with ulcerative colitis. Although it was resear… 相似文献
16.
Two new complexes [CuBr(C11H13N2O)] (1) and [Cu(NCO)(C11H13N2O)] (2) containing the tridentate Schiff base ligand, N-(1-acetyl-2-propylidene)(2-pyridylmethyl) amine which is the 1:1 condensation product of acetylacetone and 2-aminomethylpyridine, have been synthesised and characterised by elemental analysis, IR and electronic spectra, electrochemical study and single crystal X-ray diffraction study. Crystal structures reveal that the copper atom in both the complexes are in square geometry formed by the N2O donor set of the Schiff base and a bromine atom in 1 and one cyanate ligand in 2. Both bromide and isocyanate ligands act in a terminal monodentate fashion. 相似文献
17.
《Journal of Coordination Chemistry》2012,65(17):1937-1944
2-Dimethylaminoethanol (dmea) reacted with tetraaqua-bis(saccharinato)cobalt(II) and -zinc(II) in n-butanol to yield the new complexes cis-[Co(sac)2(dmea)2] (1), and cis-[Zn(sac)2(dmea)2] (2) (sac?=?saccharinate). The complexes were characterized by elemental analyses, IR spectroscopy, DTA-TG and X-ray crystallography. Both complexes are isomorphous and crystallize in the monoclinic space group P21/c. The cobalt(II) and zinc(II) ions are coordinated by two neutral dmea ligands and two sac anions in a distorted octahedral environment. The dmea ligand acts as a bidentate N, O donor through the amine N and hydroxyl O atoms, while the sac ligand exhibits non-equivalent coordination, behaving as an ambidentate ligand; one coordinates to the metal via the carbonyl oxygen atom, while the other is N-bonded. The packing of the molecules in the crystals of both complexes is achieved by aromatic π(sac)–π(sac) stacking interactions, C–H?·?π interactions and weak intermolecular C–H?·?O hydrogen bonds involving the methyl groups of dmea and the sulfonyl oxygen atoms of the sac ligands. IR and UV spectra and thermal analysis are in agreement with the crystal structures. 相似文献
18.
《Journal of Coordination Chemistry》2012,65(10):1107-1121
Four copper(II) supramolecular complexes, {[Cu(Hpb)(mal)]·H2O} n (1), (Hpb?=?2-(2-pyridyl)-benzimidazole, mal?=?maleate), [Cu4(pb)4(cro)4(MeOH)2]·2MeOH (2) (cro?=?crotonate), [Cu2(pb)(Hpb)(mac)3(MeOH)] (3) (mac?=?α-methacrylate) and [Cu(Hpb)(acr)2(H2O)] (4) (acr?=?acrylate), based on carboxylate copper(II)-aromatic ligand systems which are assembled by combination of metal coordination, hydrogen-bond and π–π interactions, have been rationally designed and synthesized. Complex 1 forms a 3D supramolecular network with open channels by extending 2D undulating sheets constructed from 1D helical chains. Complex 2 generates a 2D grid-like sheet via unusual finite-chain tetranuclear molecules, with four copper atoms arranged in a line; the unit does not extend further due to the capping effect of the terminal methanol. Complexes 3 and 4 present a 1D sinusoidal structure and a 3D columnar network with 1D ladder-shaped double chains, respectively. Interestingly, coligand Hpb, deprotonated or/and neutral in different supramolecular complexes, provides hydrogen bonding and π–π stacking interactions. In complexes 2, 3 and 4, carboxylate anions show various bridging modes, which are reflected in their magnetic properties. Weak ferromagnetic coupling (syn-anti µ-OCO) exists in 1, antiferromagnetic (syn-syn µ-OCO) and weak ferromagnetic coupling (µ-O of the??COO group) in 2 and antiferromagnetic coupling (syn-syn µ-OCO) in 3. 相似文献
19.
V. K. Gupta 《无机化学与普通化学杂志》1979,457(1):229-234
Complexes of syn-thiophene-2-aldoxime (TDH) have been synthesised and characterized on the basis of elemental analysis, molecular weight, conductance, magnetic susceptibility and i. r. spectra. These are [Co(TDH)4Cl2], [Co(TD)2], [Ni(TDH)4Cl2], [Ni(TD)2(TDH)], [Cu(CH3COO)2(TDH)]2, [Cu(TD)(OH)]2 and AgNO3 · 2TDH. In these complexes the ligand (TDH) functions as monodentate (coordinating through nitrogen atom) or bidentate (coordinating through the nitrogen and sulphur atoms). The C? S stretching frequency (of the thiophene ring) at 718 cm?1 may be taken as the criteria for the denticity of this ligand. A shift to lower frequency is observed in the complex if the ligand acts as a bidentate. However, this band is not affected if the ligand acts as monodentate. 相似文献
20.
Victor M. Deflon Daniela M. de Oliveira Gerimrio F. de Sousa Alzir A. Batista Luis R. Dinelli Eduardo E. Castellano 《无机化学与普通化学杂志》2002,628(5):1140-1144
The preparation of oxovanadium(IV, V) coordination compounds with 2‐acetylpyridine‐2‐furanoylhydrazone (Hapf) is described. [VO(apf)(acac)] was prepared from oxovanadium(IV) diacetylacetonate [VO(acac)2] by reaction with Hapf in methanol or dichloromethane. The complex is paramagnetic and its EPR spectrum is consistent with an octahedral coordination for the vanadium(IV) atom. Voltammetry studies of [VO(apf)(acac)] indicate an irreversible oxidation, in agreement with the chemical behavior of the compound in solution. The vanadium(IV) complex undergoes slow oxidation in alcoholic solution, losing the acetylacetonate ligand to form [VO2(apf)] and [V2O2(μ‐O)2(apf)2]. The crystal structures of these last compounds were determined by X‐ray diffraction methods. [V2O2(μ‐O)2(apf)2] crystallizes monoclinic [P21/c, Z = 2, a = 817.400(10), b = 1650.90(3), c = 984.70(2) pm, β = 112.7190(10)°]. The crystal structure consists of dimeric units, in which two μ‐oxo ligands subtend asymmetric bridges between the vanadium atoms in a very distorted octahedral coordination. In the crystal of [VO2(apf)], orthorhombic [Pnma, Z = 4, a = 1630.000(10), b = 675.10(4), c = 1136.40(2) pm], the vanadium(V) atom is pentacoordinated. 相似文献