Copper(<scp>ii</scp>) self-assembled clusters of bis((pyridin-2-yl)-1,2,4-triazol-3-yl)alkanes. Unusual rearrangement of ligands under reaction conditions

Гусев, А. Н.; Němec, Ivan; Herchel, Radovan; Шульгин, В. Ф.; Ryush, Irina O.; Кискин, М. А.; Ефимов, Н. Н.; Ugolkova, E. A.; Минин, В. В.; Еременко, И. Л.; Linert, Wolfgang

doi:10.1039/c8dt04816a

Cited by 8 publications

(4 citation statements)

References 43 publications

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“…It yielded, apart from three metal complexes, a polycyclic piperidine compound 10, which was a product of a complicated electron transfer between amine and Cu 2+ . It is to be noted that copper(II)-assisted transformations of organic substrates often accompany the coordination chemistry of this metal ion [28][29][30][31][32][33][34][35]. Our study provides the basis for the ongoing work on the reduction of copper(II) with piperidine and its homologs.…”

Section: Introductionmentioning

confidence: 74%

Beyond the Simple Copper(II) Coordination Chemistry with Quinaldinate and Secondary Amines

2020

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Copper(II) acetate has reacted in methanol with quinaldinic acid (quinoline-2-carboxylic acid) to form [Cu(quin)2(CH3OH)]∙CH3OH (1) (quin− = an anionic form of the acid) with quinaldinates bound in a bidentate chelating manner. In the air, complex 1 gives off methanol and binds water. The conversion was monitored by IR spectroscopy. The aqua complex has shown a facile substitution chemistry with alicyclic secondary amines, pyrrolidine (pyro), and morpholine (morph). trans-[Cu(quin)2(pyro)2] (2) and trans-[Cu(quin)2(morph)2] (4) were obtained in good yields. The morpholine system has produced a by-product, trans-[Cu(en)2(H2O)2](morphCOO)2 (5) (morphCOO− = morphylcarbamate), a result of the copper(II) quinaldinate reaction with ethylenediamine (en), an inherent impurity in morpholine, and the amine reaction with carbon dioxide. (pyroH)[Cu(quin)2Cl] (3) forms on the recrystallization of [Cu(quin)2(pyro)2] from dichloromethane, confirming a reaction between amine and the solvent. Similarly, a homologous amine, piperidine (pipe), and dichloromethane produced (pipeH)[Cu(quin)2Cl] (11). The piperidine system has afforded both mono- and bis-amine complexes, [Cu(quin)2(pipe)] (6) and trans-[Cu(quin)2(pipe)2] (7). The latter also exists in solvated forms, [Cu(quin)2(pipe)2]∙CH3CN (8) and [Cu(quin)2(pipe)2]∙CH3CH2CN (9). Interestingly, only the piperidine system has experienced a reduction of copper(II). The involvement of amine in the reduction was undoubtedly confirmed by identification of a polycyclic piperidine compound 10, 6,13-di(piperidin-1-yl)dodecahydro-2H,6H-7,14-methanodipyrido[1,2-a:1′,2′-e][1,5]diazocine.

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Section: Introductionmentioning

confidence: 74%

Beyond the Simple Copper(II) Coordination Chemistry with Quinaldinate and Secondary Amines

2020

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“…This antiferromagnetic behavior is much the same as the plot of magnetic susceptibility with temperature in another octahedral dimer, [Cu(bptrzH)(CF3SO3)H2O]2 [18]. Such typical behavior in magnetism is very common for poly-or di-nuclear copper(II) with ligand other than bptrzH due to Cu-Cu interaction and the role of counterion [12][13][14]21], ferromagnetic-antiferromagnetic coupling [15][16] and ferromagnetic domain [22]. Thus, this complex is proposed to be dimer [Cu(btrzH)Cl 2 ] 2 (as in Fig.…”

Section: Magnetic Momentmentioning

confidence: 53%

“…Another characteristic of copper(II) species is its ability to form numerous di-/poly-nuclear compounds which usually lead to typical magnetic interaction effect, that is ferro-/anti-ferromagnetic properties [12][13][14][15]. The d 9 system of Cu(II) is also well known to show structurally Jahn-Teller distortion as it has been observed in octahedral, trigonal bipyramidal, square-planar, and tetrahedral geometries, accompanying the phase transition and thus the importance in functional molecular and inorganic materials is of interest [16].…”

Section: ■ Introductionmentioning

confidence: 99%

Preparation, Electronic Properties, and Powder-XRD Structure Analysis of 3,5-Bis(pyridin-2-yl)-H-1,2,4-triazoledichloridocopper(II)

2020

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Salt of [Cu(bptrzH)Cl2], (bptrzH = 3,5-bis(pyridin-2-yl)-H-1,2,4-triazole) has been prepared and characterized its electronic spectral and magnetic properties. This salt is paramagnetic with magnetic moment, μs, being 1.77–1.78 BM at 293 K, but decreased significantly with decreasing temperature to be 0.60–0.63 BM at 90 K, indicating antiferromagnetic nature. This is associated with Cu–Cu magnetic interactions at low temperatures, and suggests that the salt adopt an octahedrally polymeric structure. The electronic spectrum of this salt reveals a strong ligand field band centered at about 13,000 cm–1 and a very strong charge transfer absorption at about 23,000–24,000 cm–1. The spectrum is better resolved at lower temperature and this is parallel to the slight change in color from yellowish-green at room temperature to bright green at low temperature (90 K). The powder XRD of this complex was refined by Le Bail method of Rietica program and found to be fit as triclinic symmetry of space group PĪ with the figure of merit: Rp = 5.02; Rwp = 7.95; Rexp = 5.40; Bragg R-Factor = 0.05; and GOF = 2.166.

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“…Triangular Cu II complexes have been largely studied in the literature, and among them, several systems present a µ 3 −X − (X = Cl − , Br − , OH − , O 2− ) bridging unit that, together with other organic auxiliary ligands enables obtaining very stable systems [1][2][3][4][5]. Due to their high stability, these triangular fragments can be used as secondary building units (SBU) in constructing several coordination polymers or MOF systems [6][7][8][9].…”

Section: Introductionmentioning

confidence: 99%

Spin Frustrated Pyrazolato Triangular CuII Complex: Structure and Magnetic Properties, an Overview

et al. 2023

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The synthesis and structural characterization of a new triangular Cu3–μ3OH pyrazolato complex of formula, [Cu3(μ3−OH)(pz)3(Hpz)3][BF4]2 (1−Cu3), Hpz = pyrazole, is presented. The triangular unit forms a quasi-isosceles triangle with Cu–Cu distances of 3.3739(9), 3.3571(9), and 3.370(1) Å. This complex is isostructural to the hexanuclear complex [Cu3(μ3−OH)(pz)3(Hpz)3](ClO4)2]2 (QOPJIP). A comparative structural analysis with other reported triangular Cu3–μ3OH pyrazolato complexes has been carried out, showing that, depending on the pyrazolato derivative, an auxiliary ligand or counter-anion can affect the nuclearity and/or the dimensionality of the system. The magnetic properties of 1−Cu3 are analyzed using experimental data and DFT calculation. A detailed analysis was performed on the magnetic properties, comparing experimental and theoretical data of other molecular triangular Cu3–μ3OH complexes, showing that the displacement of the μ3−OH− from the Cu3 plane, together with the type of organic ligands, influences the nature of the magnetic exchange interaction between the spin-carrier centers, since it affects the overlap of the magnetic orbitals involved in the exchange pathways. Finally, a detailed comparison of the magnetic properties of 1−Cu3 and QOPJIP was carried out, which allowed us to understand the differences in their magnetic properties.

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Copper(ii) self-assembled clusters of bis((pyridin-2-yl)-1,2,4-triazol-3-yl)alkanes. Unusual rearrangement of ligands under reaction conditions

Abstract: Structure and magnetic data of new Cu(ii) complexes on the bispyridyltriazolylalkanes basis are described.

Cited by 8 publications

References 43 publications

Beyond the Simple Copper(II) Coordination Chemistry with Quinaldinate and Secondary Amines

Beyond the Simple Copper(II) Coordination Chemistry with Quinaldinate and Secondary Amines

Preparation, Electronic Properties, and Powder-XRD Structure Analysis of 3,5-Bis(pyridin-2-yl)-H-1,2,4-triazoledichloridocopper(II)

Spin Frustrated Pyrazolato Triangular CuII Complex: Structure and Magnetic Properties, an Overview

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