共查询到20条相似文献,搜索用时 15 毫秒
1.
Saïda Latreche Abdelhamid Mousser Gabriele Kociok-Köhn Randolf D. Köhn Frank Schaper 《Polyhedron》2010
The unsymmetrically N-substituted N,N′-Ar2-N″-R-1,3,5-triazacyclohexanes 1–4 (Ar = ortho- or para-fluorophenyl, R = n- or iso-propyl) can be obtained in good yields from a one-step condensation reaction with excess amine. Solid state structures of 1–4 resemble closely those of their triaryl-substituted analogues. The condensation reaction to 4 was looked at by detailed NMR investigations and revealed that amine/aniline exchange is occurring in solutions containing free aniline even at ambient conditions setting up an equilibrium between all possible symmetrical and unsymmetrical triazacylcohexanes. Selective crystallisation of 4 from the solution drives the reaction to high yields of 4. Complexes 1–4 react readily with CrCl3 or CrCl3(THF)3 to form the corresponding CrCl3 complexes. The complexes are insoluble in non-polar solvents and decompose under decomplexation in coordinating solvents. 相似文献
2.
New unsymmetrically substituted hydrazines containing benzothiazole residues with substituents in the 6-position were obtained by the oxidative cyclization of substituted 1,4-diphenylthiosemicarbazides with potassium ferricyanide in alkaline aqueous alcoholic media. The reaction of these new hydrazines with trichloromethyl mercaptan gave N-(6-R-2-benzothiazolyl)-N-[p-(trichloromethylthioamidosulfonyl)phenyl]hydrazines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 765–766, June, 1971. 相似文献
3.
The oxidation of (tmeda)Pt(II)(CH(3))(2) (1, tmeda = N,N,N',N'-tetramethylethylenediamine) to (tmeda)Pt(IV)(OH)(OCH(3))(CH(3))(2) (3) by dioxygen in methanol proceeds via a two-step mechanism. The initial reaction between (tmeda)Pt(CH(3))(2) and dioxygen yields a hydroperoxoplatinum(IV) intermediate, (tmeda)Pt(OOH)(OCH(3))(CH(3))(2) (2), which reacts with a second equivalent of (tmeda)Pt(CH(3))(2) to afford the final product 3. Both 2 and 3 have been fully characterized, including X-ray crystallographic structure determinations. The effect of ligand variation on the oxidation of several dimethylplatinum(II) complexes by 2 as well as by dioxygen has been examined. 相似文献
4.
Summary Platinum(II) and Palladium(II) complexes with 2-mercaptopyrimidine, 2-thiocytosine (4-aminopyrimidine 2-thione), and isocytosine (2-amino-4-hydroxy pyrimidine) were prepared and characterised by elemental analysis, conductivity data, i.r.,1H n.m.r. and13C n.M.r. spectral studies. 2-Mercaptopyrimidine and 2-thiocytosine are coordinated to the metal ion through N(3) and C2S, thus forming a four-membered chelate ring. Isocytosine acts as a monodentate ligand and coordinates to the metal ion through N(1). All the complexes are non-electrolytes. 相似文献
5.
Tris(1-pyrazolyl)methane (HCpz3) reacts with Pt(CH3)2(COD) to form Pt(CH3)2(HCpz3), and when this complex is heated in pyridine metallation of the pyrazole ring at C(5) occurs to form Pt(CH3)(HCpz2(pzH_1))(py). A triphenylphosphine derivative, Pt(CH3)(HCpz2(pzH_1))(PPh3)2, when slowly heated to 185°C forms Pt(HCpz2(pzH_1))(C6H4PPh2); this complex has both the nitrogen and phosphorus donor ligands metallated to form six and four-membered rings, respectively. 相似文献
6.
Dirk Schmid Denis Bubrin Daniela Förster Martin Nieger Eric Roeben Sabine Strobel Dietrich Gudat 《Comptes Rendus Chimie》2010,13(8-9):998-1005
Reduction of an unsymmetrically substituted α-diimine followed by condensation with PCl3 yielded a P-chloro-N-aryl-N′-alkyl diazaphospholene which was further converted into an unsymmetrical diazaphospholium triflate by reaction with trimethylsilyl triflate. Reaction of tetramers of N-H- or N-alkyl-benzo-1,3,2-diazaphospholes with methyl triflate or triflic acid led in one step to triflate salts of unsymmetrically substituted benzo-1,3,2-diazaphospholium cations. Determination of the crystal structures of two of these derivatives by single-crystal X-ray diffraction studies revealed that individual cations and anions in the crystal lattice interact via specific electrostatic, π-stacking, or van-der-Waals type interactions to form supramolecular assemblies. Thermoanalytical measurements disclosed that benzo-diazaphospholium triflates with medium length alkyl chains melt below 100 °C and exhibit a strong tendency to form supercooled liquids. 相似文献
7.
Oliver Kaufhold F. Ekkehardt Hahn Tania Pape Alexander Hepp 《Journal of organometallic chemistry》2008,693(21-22):3435-3440
N-mesityl-N′-pyridyl-imidazolium chloride 1a and the corresponding bromide salt 1b have been deprotonated with NaH in THF giving the free N-heterocyclic carbene N-mesityl-N′-pyridyl-imidazolin-2-ylidene 2 in 80% yield (starting from 1a). Imidazolium salt 1a reacts with RuCl3 · xH2O to give a racemic mixture of dinuclear di-μ-chloro bridged ruthenium complexes [(κ2-2)2Ru(μ-Cl)2Ru(κ2-2)2]2+ [3a]2+. The carbene carbon atoms as well as the halides are arranged in cis-positions to each other whereas the nitrogen atoms adopt a trans-configuration. The di-μ-bromo bridged derivative [(κ2-2)2Ru(μ-Br)2Ru(κ2-2)2]2+ [3b]2+ was obtained from RuCl3 · xH2O and 1b. The bridging halide ligands can be removed by the reaction with silver or sodium salts of bidentate Lewis acids. Complex [3a]2+ reacts with silver pyridylcarboxylate to give a racemic mixture of the mononuclear complex [4]+. Reaction of [3a]2+ with the sodium salt of l-proline resulted in a diastereomeric mixture of complexes [5]+. The free N-heterocyclic carbene 2 reacts with [FeCl2(PPh3)2] to give after anion exchange with NaBPh4 cis/cis/trans coordinated [Fe(κ2-2)2(MeCN)2](BPh4)2 [6](BPh4)2. The molecular structures of [3b](PF6)2, [4]PF6 and [6](BPh4)2 · H2O are reported. 相似文献
8.
Rate constants and activation parameters of oxidative addition reactions of [PtMe2(2,2′-bipyridine)] with EtI and [Pt(p-MeC6H4)2 (2,2′-bipyridine)] with MeI in solvents acetone and benzene have been obtained very easily and with good accuracy from variable-temperature spectrophotometric kinetic data using a method based on nonisothermal analysis. The results are compared with those obtained by the traditional isothermal method. It is shown that there are significant advantages to measuring the reaction rates under variable-temperature kinetic conditions, as compared to the constant-temperature kinetic method. 相似文献
9.
The electrochemical reduction of the complexes [CpNi(PR3)2]+, where R = C2H5, C3H7, C4H9 or [C6Ni,(diphos)]+ and [CpNi(diars)+ in acetonitrile is described and the data are compared with those for the complexes Cp2Ni, [Ni(PR3)4]2+ and Ni(diphos)2+2. 相似文献
10.
Singh PK Kumar DN 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2006,64(4):853-858
A series of new coordination complexes of cobalt(II), nickel(II) and copper(II) with two new aroylhydrazones, 2-hydroxy-1-naphthaldehyde isonicotinoylhydrazone (H(2)L(1)) and 2-hydroxy-1-naphthaldehyde-2-thenoyl-hydrazone (H(2)L(2)) have been synthesized and characterized by elemental analysis, conductance measurements, magnetic susceptibility measurements, (1)H NMR spectroscopy, IR spectroscopy, electronic spectroscopy, EPR spectroscopy and thermal analysis. IR spectra suggests ligands acts as a tridentate dibasic donor coordinating through the deprotonated naphtholic oxygen atom, azomethine nitrogen atom and enolic oxygen atom. EPR and ligand field spectra suggests octahedral geometry for Co(II) and Ni(II) complexes and a square planar geometry for Cu(II) complexes. 相似文献
11.
The two isomeric chloromethylfuroxans have been prepared. Their structures, thermal equilibration and reaction toward thiophenoxide ion are discussed. Kinetics of the 4-methyl — 3-methyl isomer thermal conversion are also reported. 相似文献
12.
Jurgen Sleven Thomas Cardinaels Koen Binnemans Danië l Nelis Jules Mullens Dirk Hinz-Hü bner Gerd Meyer 《Liquid crystals》2003,30(2):143-148
Cobalt (II) phthalocyanines substituted with eight alkoxy chains in the peripheral (2, 3, 9, 10, 16, 17, 23, 24) positions were prepared. The alkoxy chain length was varied between n-butyloxy (C4H9O) and n-octadecyloxy (C18H37O). Studies by polarizing optical microscopy and high temperature X-ray diffraction revealed that all the complexes are liquid crystalline and that they exhibit a hexagonal columnar mesophase (Colh). Transition enthalpies were determined by differential scanning calorimetry. The clearing point could only be observed for compounds with a chain length longer than C13H27O. Both the melting and clearing points decrease with increasing chain length. The transition temperatures of these discotic metallomesogens are higher than those of the corresponding metal-free phthalocyanines, but are comparable with those of the corresponding copper (II) compounds. The thermal decomposition of the compounds was studied by thermogravimetry. 相似文献
13.
Jurgen Sleven Thomas Cardinaels Koen Binnemans Daniël Nelis Jules Mullens Dirk Hinz-Hübner 《Liquid crystals》2013,40(2):143-148
Cobalt (II) phthalocyanines substituted with eight alkoxy chains in the peripheral (2, 3, 9, 10, 16, 17, 23, 24) positions were prepared. The alkoxy chain length was varied between n-butyloxy (C4H9O) and n-octadecyloxy (C18H37O). Studies by polarizing optical microscopy and high temperature X-ray diffraction revealed that all the complexes are liquid crystalline and that they exhibit a hexagonal columnar mesophase (Colh). Transition enthalpies were determined by differential scanning calorimetry. The clearing point could only be observed for compounds with a chain length longer than C13H27O. Both the melting and clearing points decrease with increasing chain length. The transition temperatures of these discotic metallomesogens are higher than those of the corresponding metal-free phthalocyanines, but are comparable with those of the corresponding copper (II) compounds. The thermal decomposition of the compounds was studied by thermogravimetry. 相似文献
14.
15.
Bush PM Whitehead JP Pink CC Gramm EC Eglin JL Watton SP Pence LE 《Inorganic chemistry》2001,40(8):1871-1877
A series of copper(II) complexes with substituted phenanthroline ligands has been synthesized and characterized electronically and structurally. The compounds that have been prepared include the monosubstituted ligand complexes of the general formula [Cu(5-R-phen)(2)(CH(3)CN)](BF(4))(2), where R = NO(2), Cl, H, or Me, and the disubstituted ligand complex [Cu(5,6-Me(2)-phen)(2)(CH(3)CN)](BF(4))(2). The complexes [Cu(5-NO(2)-phen)(2)(CH(3)CN](BF(4))(2) (1), [Cu(5-Cl-phen)(2)(CH(3)CN)](BF(4))(2) (2), [Cu(o-phen)(2)(CH(3)CN)](BF(4))(2) (3), and [Cu(5-Me-phen)(2)(CH(3)CN)](BF(4))(2) (4) each crystallize in the space group C2/c with compounds 1, 2, and 4 comprising an isomorphous set. The disubstituted complex [Cu(5,6-Me(2)-phen)(2)(CH(3)CN)](BF(4))(2) (5) crystallizes in the space group P2(1)/c. Each structure is characterized by a distorted trigonal bipyramidal arrangement of ligands around the central copper atom with approximate or exact C(2) symmetry. The progression from electron-withdrawing to electron-donating substituents on the phenanthroline ligands correlates with less accessible reduction potentials for the bis-chelate complexes. 相似文献
16.
17.
Marie H. Darbieu Gérard Cros Dominique de Montauzon Jean -Pierre Laurent 《Transition Metal Chemistry》1982,7(3):149-151
Summary Electrophilic substitutions have been performed on the methyne carbon of NiL and [CoL,2py]ClO4 [L=N,N-bis(acetylacetone) ethylenediiminato-]. The effects of substituents (H, Cl, Br and I) on the electron distribution within the cobalt(III) complexes have been investigated through1H and13C n.m.r., i.r. spectroscopy and half-wave potential measurements 相似文献
18.
The solvatochromism observed for substituted cyanoiron complexes depends on the acceptor properties of the solvents, according to v = vo + a(AN), where ν is the measured spectral charge transfer energy and AN refers to the acceptor number scale. The parameter a was found to be strongly influenced by the solvation characteristics of the ligands compared with those of the cyanides. In H2O+S mixed solvents, preferential solvation by water was observed where S was acetone or acetonitrile, but not when S was methanol, dimethylsulfoxide, dimethylformamide or related solvents. 相似文献
19.
The preparation of the Schiff's bases derived from 1,2-diaminoethane and a series of 5-alkyl substituted-1,1,1-trifluoropentan-2:4-diones is described, including the elusive compound obtained from 1,1,1-trifluoro-5,5,5-trimethylpentan-2:4-dione, and trivially denoted as H2[en(TPM)2]. Gas chromatography of the copper complexes of these ligands shows increasing retention times as the size of the alkyl substituent is increased, with the exception of Cu[en(TPM)2] which is unusually volatile and has a much reduced retention time. It is most probable that this graat difference in properties occurs because of the considerable steric hindrance of the tert-butyl groups in the original β-diketone, which prevents the normal condensation reaction with 1,2-diaminoethane taking place. The properties of the metal complexes of H2[en(TPM)2] make them ideally suited to quantitative gas chromatography. 相似文献
20.
L. D. Popov Yu. P. Tupolova S. I. Levchenkov V. V. Lukov V. A. Kogan 《Russian Journal of Coordination Chemistry》2007,33(3):208-212
A series of novel mono-and binuclear copper(II) complexes with substituted salicylaldehyde acylhydrazones H2L of the formula CuL · xH2O (x = 0 and 1) and [Cu(HL)](ClO4)(CH3OH) were synthesized. The isolated dimeric complexes of copper acetate were found to exist as isomers with different bridging atoms. In dimers showing a superexchange between the paramagnetic centers through bridging phenoxide O atoms, the antiferromagnetic exchange couplings were much stronger than those in complexes with bridging O atoms of the a-oxyazine fragment. 相似文献