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1.
Cheng JW  Zheng ST  Ma E  Yang GY 《Inorganic chemistry》2007,46(25):10534-10538
A new series of heterometallic lanthanide(III)-copper(I) coordination polymers Ln2(bdc)2(ina)2(H2O)2Cu x X (Hina = isonicotinic acid; H2bdc = 1,2-benzenedicarboxylic acid; Ln = Eu (1), Sm (2), Nd (3), X = ClO4-; Ln = Nd (4), X = Cl-) have been hydrothermally synthesized in the presence/absence of HClO4. Both compounds are isostructural and contained two distinct units of 2D Ln-bdc layers and linear [Cu(ina)2]-. The linear [Cu(ina)2]- complexes act as pillars and further link the Ln-bdc layers resulting in four heterometallic metal-organic frameworks, which represent the first pillared-layer 3d-4f framework with two distinct types of channels along the b and c axes. The compounds can be specified by the Schl?fli symbol (47.63)(47.68) as a novel 3D (5,6)-connected net. Furthermore, the IR, TGA, PXRD, and UV-vis spectral and luminescent properties of 1-4 were also studied.  相似文献   

2.
Gold(III) and palladium(II) extraction from 3 mol/L hydrochloric acid solutions with (RS)-1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole (chloroform diluent) was studied. Optimal extraction conditions were found. Coordination mechanism of extraction was established on the basis of IR and NMR spectra of extracted compounds. Concentrational extraction constants were calculated and thermodynamic parameters of the process were assessed.  相似文献   

3.
The 1H-nmr data of some (Z)-α-(p-substituted-phenyl)-β-(2-furyl), -(2-pyrrolyl), and -(N-methyl-2-pyrrolyl)-acrylonitriles have been investigated to indicate the preferred conformation and to establish the conformational preferences of the β-heterocyclic ring. The ultraviolet spectra have been discussed in order to obtain information about the chromophores responsible for the absorption. The infrared spectra have been analyzed for the identification of the main absorption frequencies of cyano and ethylenic groups and to assign the characteristic absorption bands to specific normal vibrations of the heteroaromatic nuclei.  相似文献   

4.
The formation and extraction of ion-associate complexes between the vanadium(V)-4-(2-thiazolylazo)resorcinol (TAR) anionic chelate and the cations of some mono-and ditetrazolium salts {3-(4,5-dimethyl-2-thiazol)-2,5-diphenyl-2H-tetrazolium bromide (Thiazolyl blue, MTT), 3-(2-naphtyl)-2,5-diphenyl-2H-tetrazolium chloride (Tetrazolium violet), 2-(4-iodophenyl)-3-(4-nitrophenyl)-5-phenyl-2H-tetrazolium chloride (Iodonitrotetrazolium chloride), 3,3′-[3,3′-dimetoxy(1,1′-biphenyl)-4,4′-diyl]-bis[2,5-diphenyl-2H-tetrazolium] chloride (Tetrazolium blue chloride) and 3,3′-(3,3′-dimetoxy-4,4′-biphenylene)bis[2-(4-nitrophenyl)-5-phenyl-2H-tetrazolium chloride] (Nitro blue tetrazolium chloride)} have been studied. The optimum extraction conditions have been found. The composition of the V-TAR-monotetrazolium and V-TAR-ditetrazolium complexes extracted into chloroform has been determined to be 1:2:3 and 2:4:3 respectively. The extraction, distribution and association constants, and the recovery factors have been calculated. The relationship between the molecular weight of tetrazolium cations, and the association constants of their complexes has been discussed. The special behavior of the tetrazolium cations, containing-NO2 groups has been noticed. The effects of foreign ions and reagents on the extraction of vanadium with TAR and the best tetrazolium salt-MTT have been studied. A sensitive, selective, simple and fast method for the determination of vanadium has been developed.   相似文献   

5.
Extraction of hydrochloric and nitric acid with 1-{[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]-methyl}-1H-1,2,4-triazole (propiconazole) and hydrochloric acid with (RS)-1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-yl-methyl)-pentan-3-ol (tebuconazole) was studied. It is established that extraction of acids proceeds with the formation of monosolvates as an exothermic process. Effective extraction constants of acids are evaluated. By means of the IR and 1H NMR spectroscopy it was shown that the protonaccepting center of tebuconazole is N4 atom of the triazole ring.  相似文献   

6.
Cathinones belong to a group of compounds of great interest in the new psychoactive substances (NPS) market. Constant changes to the chemical structure made by the producers of these compounds require a quick reaction from analytical laboratories in ascertaining their characteristics. In this article, three cathinone derivatives were characterized by X-ray crystallography. The investigated compounds were confirmed as: 1-[1-(4-methylphenyl)-1-oxohexan-2-yl]pyrrolidin-1-ium chloride ( 1 , C17H26NO+·Cl?, the hydrochloride of 4-MPHP), 1-(4-methyl-1-oxo-1-phenylpentan-2-yl)pyrrolidin-1-ium chloride ( 2 ; C16H24NO+·Cl?, the hydrochloride of α-PiHP) and methyl[1-(4-methylphenyl)-1-oxopentan-2-yl]azanium chloride ( 3 ; C13H20NO+·Cl?, the hydrochloride of 4-MPD). All the salts crystallize in a monoclinic space group: 1 and 2 in P21/c, and 3 in P21/n. To the best of our knowledge, this study provides the first detailed and comprehensive crystallographic data on salts 1 – 3 .  相似文献   

7.
The nature of the chemical bonding in the 1:1 complexes formed by the fourth period transition metals (Sc, ..., Cu) with 14 electrons (N(2), CN(-), C(2)H(2)) and 10 electrons (NH(3), H(2)O, F(-)) ligands has been investigated at the ROB3LYP/6-311+G(2d) level by the ELF topological approach. The bonding is ruled by the nature of the ligand. The 10 electrons and anionic ligands are very poor electron acceptors and therefore the interaction with the metal is mostly electrostatic and for all metal except Cr the multiplicity is given by the [Ar]c(n)() configuration of the metallic core (n = Z - 20). The electron acceptor ligands which have at least a lone pair form linear or bent complexes involving a dative bond with the metal and the rules proposed previously for monocarbonyls hold. In the case of ethyne, it is not possible to form a linear complex and the cyclic C(2)(v)() structure imposed by symmetry possesses two covalent M-C bonds, therefore the multiplicity is given by the local core configuration [Ar]c(n)() for all metals except Mn and Ni.  相似文献   

8.
The 3,5-di-tert-butylpyrazolato (3,5-tBu(2)pz) derivatives of aluminum [(eta(1),eta(1)-3,5-tBu(2)pz)(mu-Al)R(1)R(2)](2) (R(1) = R(2) = Me 1; R(1) = R(2) = Et, 2; R(1) = R(2) = Cl, 3; R(1) = R(2) = I, 4; [(eta(2)-3,5-tBu(2)pz)(3)Al], 5; [Al(2)(eta(1),eta(1)-3,5-tBu(2)pz)(2)(mu-E)(C triple bond CPh)(2)] (E = S (6), Se (7), Te (8)) have been prepared in good yield. Compounds 1 and 2 were obtained by the reactions of H[3,5-tBu(2)pz] with Me(3)Al and Et(3)Al, respectively. Reaction of [(eta(1),eta(1)-3,5-tBu(2)pz)(mu-Al)H(2)](2) with the pyrazole H[3,5-tBu(2)pz] gave [(eta(2)-3,5-tBu(2)pz)(3)Al] (5). The reaction of [(eta(1),eta(1)-3,5-tBu(2)pz)(mu-Al)R(2)](2) (R = H, Me) and I(2) yielded 4, while the reaction of 1 equiv of K[3,5-tBu(2)pz] and AlCl(3) afforded 3. In addition, the reaction of [Al(2)(eta(1),eta(1)-3,5-tBu(2)pz)(2)(mu-E)H(2)] and HC triple bond CPh gave 6, 7, and 8. All compounds have been characterized by elemental analysis, NMR, and mass spectroscopy. The molecular structure analyses of compounds 1, 3, 6, and 7 by X-ray crystallography showed that complexes 1 and 3 are dimeric with two eta(1),eta(1)-pyrazolato groups in twisted conformation while 6 and 7 with two eta(1),eta(1)-pyrazolato groups display a boat conformation.  相似文献   

9.
Palladium(II) extraction from nitric acid solutions with 1-{[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]-methyl}-1H-1,2,4-triazole in toluene is studied. The reagent efficiently extracts palladium(II) from 0.2–6 M HNO3 by a coordination mechanism yielding the complex Pd2(NO3)4 S 3 in the organic phase. The reagent can be used for selective separation of palladium(II) from nickel(II), copper(II), and iron(III) in the specified aqueous phase acidity range.  相似文献   

10.
The extraction of gallium(III) with 1-{[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2- yl]methyl}-1H-1,2,4-triazole from hydrochloric acid solutions into toluene was studied. It was found that gallium( III) was efficiently extracted from 5–10 M solutions of HCl by the anion-exchange mechanism. The following metal extraction order was determined in the above aqueous phase acidity range: Ga(III) > In(III) > Al(III). The concentration constants and the thermodynamic parameters of the reaction of gallium(III) extraction from 6 M solutions of HCl at 25 °C were calculated.  相似文献   

11.
The well-known tetradentate ligand 1,2-bis(pyridine-2-carboxamido)benzenate(2-), (bpb)2-, and its 4,5-dichloro analogue, (bpc)2-, are shown to be "noninnocent" ligands in the sense that in coordination compounds they can exist in their radical one- and diamagnetic two-electron-oxidized forms (bpbox1)- and (bpbox2)0 (and (bpcox1)- and (bpcox2)0), respectively. Photolysis of high-spin [(n-Bu)4N][FeIII(bpb)(N3)2] and its (bpc)2- analogue in acetone solution at room temperature generates the diamagnetic dinuclear complex [(n-Bu)4N][FeIV2(mu-N)(bpb)2(N3)2] and its (bpc)2- analogue; the corresponding cyano complex [(n-Bu)4N][FeIV2(mu-N)(bpb)2(CN)2] has been prepared via N3- substitution by CN-. Photolysis in frozen acetonitrile solution produces a low-spin ferric species (S = 1/2) which presumably is [FeIII(bpbox2)(N)(N3)]-, as has been established by EPR and M?ssbauer spectroscopy. The mononuclear complexes [(n-Bu)4N][FeIII(bpb)(CN2)] (low spin), [Et4N][CoIII(bpb)(CN)2] and Na[CoIII(bpc)-(CN)2].3CH3OH can be electrochemically or chemically one-electron-oxidized to give [FeIII(bpbox1)(CN)2]0 (S = 0), [CoIII(bpbox1)(CN)2]0 (S = 1/2), and [CoIII(bpcox1)(CN)2]0 (S = 1/2). All complexes have been characterized by UV-vis, EPR, and M?ssbauer spectroscopy, and their electro- and magnetochemistries have been studied. The crystal structures of [(n-Bu)4N][FeIII(bpb)(N3)2].1/2C6H6CH3, Na[FeIII(bpb)(CN)2], Na[CoIII(bpc)(CN)2].3CH3OH, [(n-Bu)4N][FeIV2(mu-N)(bpb)2(CN)2], and [(n-Bu)4N][FeIV2(mu-N)(bpb)(N3)2] have been determined by single-crystal X-ray diffraction.  相似文献   

12.
The rate constant, k, for the homogeneous electron transfer (self-exchange) reaction between the diamagnetic bis(maleonitriledithiolato)nickel dianion, [Ni(mnt) 2] (2-), and the paramagnetic monoanion, [Ni(mnt) 2] (1-), has been determined in acetone and nitromethane (CH 3NO 2) using (13)C NMR line widths at 22 degrees C (mnt = 1,2-S 2C 2(CN) 2). The values of k (2.91 x 10 (6) M (-1) s (-1) in acetone, 5.78 x 10 (6) M (-1) s (-1) in CH 3NO 2) are faster than those for the electron transfer reactions of other Ni(III,II) couples; the structures of [Ni(mnt) 2] (1-) and [Ni(mnt) 2] (2-) allow for a favorable overlap that lowers the free energy of activation. The values of k are consistent with the predictions of Marcus theory. In addition to k, the spin-lattice relaxation time, T 1e, of [Ni(mnt) 2] (1-) is obtained from the NMR line width analysis; the values are consistent with those predicted by spin relaxation theory.  相似文献   

13.
[structure: see text] Oligonucleotides with novel modifications, 2'-O-[2-(amino)-2-oxoethyl] (2'-O-NAc), 2'-O-[2-(methylamino)-2-oxoethyl] (2'-O-NMAc), 2'-O-[2-(dimethylamino)-2-oxoethyl] (2'-O-DMAc), and 2'-O-[2-[[2-(dimethylamino)ethyl]amino]-2-oxoethyl] (2'-O-DMAEAc), have been synthesized. These modified oligonucleotides exhibit high binding affinity to complementary RNA (and not to DNA) and considerably enhance the nuclease stability of oligonucleotides with t(1/2) > 24 h.  相似文献   

14.
The corresponding 1-(2-quinoxalyl)-, 1-[3,5-di(trifluoromethyl)phenyl]-, and 1-ethoxycarbonyl-3-methyl-4-oxo-4,5,6,7-tetrahydroindazoles have been obtained from reactions of 2-acetyl-1,3-cyclohexanedione, its 5,5-dimethyl and 5-(2-furyl) derivatives, with 2-hydrazinoquinoxaline, 3,5-di(trifluoromethyl)phenylhydrazine, and ethoxycarbonylhydrazine. On interaction with ethoxycarbonylhydrazine the intermediate 2-[1-(-ethoxycarbonyl)hydrazino]ethylidene-1,3-cyclohexanediones were also isolated. From the potassium salt of 2-formyldimedone and 2-carboxyphenylhydrazine hydrochloride, 2-(2-carboxyphenyl)hydrazinomethylene-5,5-dimethyl-1,3-cyclohexanedione was obtained, the cyclization of which in ethanol in the presence of HCl led to 1-(2-carboxyphenyl)- and 1-(2-ethoxycarbonylphenyl)-6,6-dimethyl-4-oxo-4,5,6,7-tetrahydroindazole.  相似文献   

15.
In an attempt to generate nicotinic acetylcholine receptor (nAChR) ligands selective for the alpha4beta2 and alpha7 subtype receptors we designed and synthesized constrained versions of anabasine, a naturally occurring nAChR ligand. 2-(Pyridin-3-yl)-1-azabicyclo[2.2.2]octane, 2-(pyridin-3-yl)-1-azabicyclo[3.2.2]nonane, and several of their derivatives have been synthesized in both an enantioselective and a racemic manner utilizing the same basic synthetic approach. For the racemic synthesis, alkylation of N-(diphenylmethylene)-1-(pyridin-3-yl)methanamine with the appropriate bromoalkyltetrahydropyran gave intermediates which were readily elaborated into 2-(pyridin-3-yl)-1-azabicyclo[2.2.2]octane and 2-(pyridin-3-yl)-1-azabicyclo[3.2.2]nonane via a ring opening/aminocyclization sequence. An alternate synthesis of 2-(pyridin-3-yl)-1-azabicyclo[3.2.2]nonane via the alkylation of N-(1-(pyridin-3-ylethylidene)propan-2-amine has also been achieved. The enantioselective syntheses followed the same general scheme, but utilized imines derived from (+)- and (-)-2-hydroxy-3-pinanone. Chiral HPLC shows that the desired compounds were synthesized in >99.5% ee. X-ray crystallography was subsequently used to unambiguously characterize these stereochemically pure nAChR ligands. All compounds synthesized exhibited high affinity for the alpha4beta2 nAChR subtype ( K i < or = 0.5-15 nM), a subset bound with high affinity for the alpha7 receptor subtype ( K i < or = 110 nM), selectivity over the alpha3beta4 (ganglion) receptor subtype was seen within the 2-(pyridin-3-yl)-1-azabicyclo[2.2.2]octane series and for the muscle (alpha1betagammadelta) subtype in the 2-(pyridin-3-yl)-1-azabicyclo[3.2.2]nonane series.  相似文献   

16.
The 2,2,2-crypt salts of the Tl4Se8(4-) and [Tl2Se4(2-)]infinity1 anions have been obtained by extraction of the ternary alloy NaTl0.5Se in ethylenediamine (en) in the presence of 2,2,2-crypt and 18-crown-6 followed by vapor-phase diffusion of THF into the en extract. The [2,2,2-crypt-Na]4[Tl4Se8].en crystallizes in the monoclinic space group P2(1)/n, with Z = 2 and a = 14.768(3) angstroms, b = 16.635(3) angstroms, c = 21.254(4) angstroms, beta = 94.17(3) degrees at -123 degrees C, and the [2,2,2-crypt-Na]2[Tl2Se4]infinity1.en crystallizes in the monoclinic space group P2(1)/c, with Z = 4 and a = 14.246(2) angstroms, b = 14.360(3) angstroms, c = 26.673(8) angstroms, beta = 99.87(3) degrees at -123 degrees C. The TlIII anions, Tl2Se6(6-) and Tl3Se7(5-), and the mixed oxidation state TlI/TlIII anion, Tl3Se6(5-), have been obtained by extraction of NaTl0.5Se and NaTlSe in en, in the presence of 2,2,2-crypt and/or in liquid NH3, and have been characterized in solution by low-temperature 77Se, 203Tl, and 205Tl NMR spectroscopy. The 1J(203,205Tl-77Se) and 2J(203,205Tl-203,205Tl) couplings of the three anions have been used to arrive at their solution structures by detailed analyses and simulations of all spin multiplets that comprise the 205,203Tl NMR subspectra arising from natural abundance 205,203Tl and 77Se isotopomer distributions. The structure of Tl2Se6(6-) is based on a Tl2Se2 ring in which each thallium is bonded to two exo-selenium atoms so that these thalliums are four-coordinate and possess a formal oxidation state of +3. The Tl4Se8(4-) anion is formally derived from the Tl2Se6(6-) anion by coordination of each pair of terminal Se atoms to the TlIII atom of a TlSe+ cation. The structure of the [Tl2Se4(2-)]infinity1 anion is comprised of edge-sharing distorted TlSe4 tetrahedra that form infinite, one-dimensional [Tl2Se42-]infinity1 chains. The structures of Tl3Se6(5-) and Tl3Se7(5-) are derived from Tl4Se4-cubes in which one thallium atom has been removed and two and three exo-selenium atoms are bonded to thallium atoms, respectively, so that each is four-coordinate and possesses a formal oxidation state of +3 with the remaining three-coordinate thallium atom in the +1 oxidation state. Quantum mechanical calculations at the MP2 level of theory show that the Tl2Se6(6-), Tl3Se6(5-), Tl3Se7(5-), and Tl4Se8(4-) anions exhibit true minima and display geometries that are in agreement with their experimental structures. Natural bond orbital and electron localization function analyses were utilized in describing the bonding in the present and previously published Tl/Se anions, and showed that the Tl2Se6(6-), Tl3Se6(5-), Tl3Se7(5-), and Tl4Se8(4-) anions are electron-precise rings and cages.  相似文献   

17.
Condensation of 3-methyl-2-azafluorene with 2-formylfluorene results in the formation of a compound containing a polyconjugated system and two acidic CH centers, namely, 1-(fluoren-2-yl)-2-(2-azafluoren-3-yl)ethene. The conversions of this compound upon treatment with alkali have been studied by electronic absorption spectroscopy. The methyl iodide derivative of this base was used as an intermediate in the preparation of a pseudo-azulene, 1-(fluoren-2-yl)-2-(2H, 2-methylindeno[2,3-c]pyridine)ethene.Translated from Khimiya Geterotsiklicheskikh Soedinenii No. 5, pp. 657–659, May, 1987.  相似文献   

18.
Hitherto unknown 3-(2H-Indazol-2-yl)-2H[1] benzopyran-2-ones (4a-f) have been synthesized under the trithyl phosphite (TEP) mediated reaction conditions of 3-[[(2-nitro-phenyl)-methylene]amino]-2H-1-benzopyran-2-ones (3a-f), obtained by the condensation of 3-amino coumarins (1a-f) with 2-nitro-benzaldehyde (2).  相似文献   

19.
Copper(II) extraction with 1-“[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]-methyl”-1H-1,2,4-triazole in toluene from hydrochloric acid solutions is studied. It is shown that copper(II) is most efficiently extracted with this reagent from 3–5 M HCl solutions. For aqueous acidity of 3 mol/L HCl, the extraction is an exothermal process and follows the coordination mechanism. The anion-exchange extraction mechanism predominates where HCl concentrations is greater than 6 mol/L. The studied reagent can be used for the selective separation of copper(II) from nickel(II) and cobalt(II) at aqueous acidities of up to 4 mol/L HCl.  相似文献   

20.
Cycloaddition to 1-(4,6-dimethylpyrimidin-2-yl)- and 1-(4,6-dimethoxy-s-triazin-2-yl)-3-oxidopyridinium betaines across the 2,6-positions of the pyridine rings with indene, acenaphthylene and ethyl cinnamate gave substituted 8-aza[3.2.1]bicycIooct-3-en-2-ones, whereas the [6π + 4π] cycloaddition reaction with 6,6-dimethylfulvene gave a tricyclo[6.3.1.02.6]dodeca-2,(6),4,9-trien-11-one. Structural and configurational assignments of the cycloadducts were deduced from 1H nmr and ir spectral data.  相似文献   

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