- One-dimensional copper(II) compound with a double out-of-plane carboxylato-bridge - Another polymorphic form of Cu(pyridine-2-carboxylate)2
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The crystal and molecular structure of a blue-violet copper(II) compound of the formula Cu(2-pic)2 (2-pic = 2-picolinate or pyridine-2-carboxylate ion) was determined. Its structure consists of a copper atom lying in the centre of symmetry, trans square-planar coordinated via two pyridine nitrogens and the carboxylate oxygen atoms of the two picolinate anions. The bonding interaction between the copper and the oxygen of carboxylate atoms of neighboring planes completes the square-planar coordination to a strongly tetragonally distorted octahedral stereochemistry (CuN2 O2 O2′ chromophore), when long axial Cu-O bond distances are included. This intermolecular interaction, with the Cu?Cu distance of 5.163 ?, is weak, but permits to define the structure as a one-dimensional chain with a double out-of-plane carboxylate bridge. The magnetic behavior of the compound can be explained as a result of magnetic exchange within the chain through long Cu-O axial bonds (J = -0.73 cm-1) and a superexchange pathway through the hydrogen bond network between adjacent molecules (zJ′ = -0.06 cm-1). The magnitude and the nature of the exchange coupling are explained on the basis of the structural data results.
- Zurowska, Bogumi?a,Mroziński, Jerzy,Ciunik, Zbigniew
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- Alcoholysis of 2,2'-pyridil, (2-C5H4N)C(O)C(O)(2-C5H4N), iin the presence of copper(II): A family of planar pentanuclear copper(II) complexes stabilized by [(2-C5H4N)C(O)(OR)C(O)(OR)(2-C5H4N)]2- and carboxylate ligands
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'Blends' of 2,2'-pyridil, (2-C5>H4>N)C(O)C(O)(2-C5>H4>N), and carboxylate ligands, R'CO2-, in alcohols (ROH) at room temperature are used to produce three clusters of the general formula [Cu5(OH)2{[(2-C5H4N)C(O)-(OR)C(O)(OR)(2-C5H4N)}2>(O2>CR')4>(ROH)2 >]. The five Cu(II) atoms are coplanar, exhibiting a rectangular arrangement of four metal ions with the fifth at the center of the rectangle. The representative complex with R = Et and R' = Me exhibits antiferromagnetic behavior.
- Papaefstathiou, Giannis S.,Raptopoulou, Catherine P.,Tsohos, Alexandros,Terzis, Aris,Bakalbassis, Evangelos G.,Perlepes, Spyros P.
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- Access to a CuII-O-CuII motif: Spectroscopic properties, solution structure, and reactivity
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We report a complex with a rare CuII-O-CuII structural motif that is stable at room temperature, which allows its in-depth characterization by a variety of spectroscopic methods. Interest in such compounds is fueled by the recent discovery that a CuII-O-Cu II species on the surface of Cu-ZSM-5 is capable of oxidizing methane to methanol, and this in turn ties into mechanistic discussions on the methane oxidation at the dicopper site within the particulate methane monooxygenase. For the synthesis of our Cu2O complex we have developed a novel, neutral ligand system, FurNeu, exhibiting two N-(N′,N′-dimethylaminoethyl) (2-pyridylmethyl)amino binding pockets connected by a dibenzofuran spacer. The reaction of FurNeu with CuCl yielded [FurNeu](Cu2(μ-Cl))(CuCl 2), 1, demonstrating the geometric potential of the ligand to stabilize Cu-X-Cu moieties. A CuI precursor with weakly coordinating anions was chosen in the next step, namely [Cu(NCCH3) 4]OTf, which led to the formation of [FurNeu](Cu(NCCH 3))2(OTf)2, 3. Treatment of 3 with O 2 or PhIO led to identical green solutions, whose UV-vis spectra were markedly different from the one displayed by [FurNeu](Cu)2(OTf) 4, 4, prepared independently from FurNeu and Cu(OTf)2. Further investigations including PhIO consumption experiments, NMR and UV-vis spectroscopy, HR-ESI mass spectrometry, and protonation studies led to the identification of the green product as [FurNeu](Cu2(μ-O))(OTf) 2, 5. DOSY NMR spectroscopy confirmed its monomeric character. Over longer periods of time 5 decomposes to give [Cu(picoloyl)2], formed through an oxidative N-dealkylation reaction followed by further oxidation of the ligand. Due to its slow decomposition reaction, all attempts to crystallize 5 failed. However, its structure in solution could be determined by EXAFS analysis in combination with DFT calculations, which revealed a Cu-O-Cu angle that amounts to 105.17. Moreover, TDDFT calculations helped to rationalize the UV-vis absorptions of 5. The reactivity of complex 5 with 2,4-di-tert- butylphenol, DTBP, was also investigated; the initially formed biphenol product, TBBP, was found to further react in the presence of excessive O2 to yield 2,4,7,9-tetra-tert-butyloxepino[2,3-b]benzofuran, TBOBF, via an intermediate diphenoquinone. It turned out that 5, or its precursor 3, can even be employed as a catalyst for the oxidation of DTBP to TBBP or for the oxidation of TBBP to TBOBF.
- Haack, Peter,Kaergel, Anne,Greco, Claudio,Dokic, Jadranka,Braun, Beatrice,Pfaff, Florian F.,Mebs, Stefan,Ray, Kallol,Limberg, Christian
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- Synthesis, spectroscopic and magnetostructural evidence for the formation of Cu(II) complexes of pyridyl-2-carboxylate (2-pca) and quinolyl-2-carboxylate (2-qca) as a result of a novel oxidative P-dealkylation reaction of diethyl 2-pyridylmethylphosphonate (2-pmpe) and diethyl 2-quinolylmethylphosphonate (2-qmpe) ligands
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The interaction of diethyl 2-pyridylmethylphosphonate (2-pmpe) ligand with CuX2 salts unexpectedly leads to the formation of compounds of the formula Cu(2-pca)2 [X=Cl- (1), CH3COO - (3)], and Cu(2-pca)Cl [X=Cl- (2)] (2-pca=pyridine-2- carboxylate ion). The diethyl 2-quinolylmethylphosphonate ligand (2-qmpe) reacts with CuX2 salts to similarly yield compounds of stoichiometry Cu(2-qca)2·H2O (X=ClO4- (4)], and for X=Cl Cu(2-qca)2·H2O (5) and Cu(2-qca)Cl (6), (2-qca=quinoline-2-carboxylate ion). These compounds are products of a novel oxidative P-dealkylation reaction, which takes place on 2-pmpe and 2-qmpe ligands under the used conditions. The compounds were characterized by infrared, ligand field, EPR spectroscopy and magnetic studies. Cu(2-pca)2 exists in two crystalline forms, a blue form (1) and a violet form (3). For 3 the single-crystal structure was determined. The copper atom is four-coordinated in a square-planar geometry. The stack between related (and hence parallel) pca moieties involves interatomic distances of 3.27 A?. Cu(2-qca)2·H2O also exists in two forms, a green (4) and a blue-green (5). Both these complexes are five coordinated, involve the same CuN2O3 chromophore and are examples of the distortion isomers. Variable-temperature magnetic susceptibility measurements (1.9-300 K) have shown that the antiferromagnetic coupling observed is much stronger in 6 than in 1, 3, 4 and 5. For 2 a ferromagnetic exchange occurs.
- Zurowska, Bogumi?a,Ochocki, Justyn,Mroziński, Jerzy,Ciunik, Zbigniew,Reedijk, Jan
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- Metal(II)-promoted hydrolysis of pyridine-2-carbonitrile to pyridine-2-carboxylic acid. The structure of [Cu(pyridine-2-carboxylate)2] · 2H2O
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Pyridine-2-carbonitrile (2-CNpy) undergoes Cu(II) or Co(II)-promoted hydrolysis to pyridine-2-carboxamide (piaH) and/or pyridine-2-carboxylic acid (pycH). The pathway of pycH formation depends on the presence of 2-amino-2-hydroxymethyl-1,3-propanediol (AL1) and on the central atom. In the absence of AL1, Co(II) or Cu(II) ions mediate piaH formation under mild reaction conditions in the first hydrolytic step. Cu(II) ions assist in piaH transformation to pycH by subsequent reflux. In the presence of AL1 and Co(II), a Co(II) complex containing pyoxaL1 (2-(2-pyridinyl)-4,4-bis(hydroxymethyl)-2-oxazoline) is formed in the first stage; subsequent decomposition of pyoxaL1 under the reflux yields pycH. Under similar conditions, no solid Cu(II) complex with pyoxaL1 can be isolated, but a Cu(II) complex with coordinated pyc- anions precipitates from the reaction mixture. The synthesis, spectral and magnetic properties of the complexes [Co(H2O)2 (piaH)2]Cl2, [Co(H2O)2(pyc)2] · 2H2O, [Cu(H2O)2(piaH)2]Cl2, [Cu(pyc)2] and [Cu(pyc)2] · 2H2O, including the structure determination of the latter one, are described.
- Segl'A,Jamnicky,Koman,Sima,Glowiak
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- Electrochemical Synthesis and Characterization of Copper(II) and Zinc(II) Coordination Compounds with Nicotinic and Picolinic Acids
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Abstract: New methods for the electrochemical synthesis of copper(II) and zinc(II) coordination compounds with pyridinecarboxylic acids (nicotinic and picolinic) have been developed. The resulting compounds were characterized by quantitative analysis and IR spectroscopy. The vibrational frequencies of the synthesized compounds were calculated by a DFT quantum-chemical method, and the experimental IR spectra were interpreted on this basis. It was found that pyridinecarboxylate ions in all cases are coordinated both at the nitrogen atom and at the carboxylate group, however, in the case of nicotinic acid, this leads to the formation of coordination polymers, whereas for picolinic acid, the formation of mononuclear complexes is typical.
- Andriychenko, E. O.,Bespalov, A. V.,Bovyka, V. E.,Bukov, N. N.,Zelenov, V. I.
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p. 1697 - 1705
(2021/11/01)
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- Synthesis and structural chemistry of CoII, CuII, CuI and PdII complexes containing a flexible monoselenoether ligand
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Monoselenoether ligand [PySeCH2Py] (L) reacts with CoCl2, CuCl2, CuI and Pd(OAc)2 resulting in the formation of molecular or polymeric complexes. The synthesis and structural elucidation of the complexes [CoCl2(L)] (1), [Cu2Cl4(L)2] (2a), [CuCl2(L)] (2b), [Cu2Cl2(PySe)2] (2c), [Cu(2-PyCOO)2] (2d), [Cu2I2(L)2] (3), [Cu2I2(L)]n (4) and [Pd2(CH3COO)2(PySeCHPy)2]·7H2O (5) demonstrate the versatility of this class of pyridylselenium ligands. For all compounds, the ligand offers N and/or Se atoms as donors and, in the case of 5, the ligand also builds C-Pd bonds to generate a cyclometallated palladium(ii) complex.
- Cargnelutti, Roberta,Delgado, Cássia P.,Cervo, Rodrigo,Tirloni, Bárbara,Burrow, Robert A.,Lang, Ernesto S.
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supporting information
p. 17185 - 17189
(2018/11/01)
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- Coordination behavior of 3,4-bis(2-pyridylmethylthio)toluene with copper(II) ions: Synthesis, structural characterization and reactivity, and DNA binding study of the dinuclear copper(II) complex
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On reaction of different copper(II) salts with 3,4-bis(2-pyridylmethylthio) toluene (L) having neutral tetradentate NSSN donor set in different chemical environments, two mononuclear copper(II), one dinuclear copper(I) and one dinuclear copper(II) complex
- Sarkar, Sandipan,Sen, Supriti,Dey, Sourav,Zangrando, Ennio,Chattopadhyay, Pabitra
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p. 3157 - 3163
(2011/02/18)
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- Synthesis and magnetic property of a dual μ-[N(CN)2] bridged copper(II) supramolecule with dinuclear unit
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A dicyanamide (dca) Cu(II) supramolecular complex constructed by hydrogen-bond interactions and weak Cu-N bond interactions has been prepared and the structure was determined by X-ray diffraction analysis. The magnetic studies indicate that strong antiferromagnetic interactions exist between two Cu(II) ions of the dca-bridged dimer.
- Shi, Qian,Hu, Mao-Lin,Xiao, Hong-Ping,Li, Xin-Hua
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p. 1169 - 1172
(2008/10/09)
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- Reactions of 1,2-Dicarbonyls with Metallic Copper under Argon and Dioxygen. Oxidative C-C Bond Scission by Metellic Copper
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1,2-Diketones such as benzil, 2,2'-furil, and di(2-pyridyl)diketone react with metallic copper in pyridine under argon by electron transfer from the copper to the 1,2-diketones, giving semidionato copper(I) and μ-enediolato-dicopper(I) complexes in low equilibrium concentrations as detected by e.s.r. and visible absorption spectra.Under dioxygen with a 1:1 stoichiometry of copper to 1,2-diketones, a facile oxidative C-C bond cleavage occurs to give well defined carboxylate copper(II) complexes with ligands such as pyridine, 2,2'-bipyridine, and N,N,N',N'-tetramethylethylenediamine.
- Speier, Gabor,Tyeklar, Zoltan
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p. 2663 - 2668
(2007/10/02)
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