14604-51-4Relevant academic research and scientific papers
Reversible Cu4 ? Cu6 core interconversion and temperature induced single-crystal-to-single-crystal phase transition for copper(I) carboxylate
Filatov, Alexander S.,Hietsoi, Oleksandr,Sevryugina, Yulia,Gerasimchuk, Nikolay N.,Petrukhina, Marina A.
, p. 1626 - 1633 (2010)
The first example of a reversible [Cu4] ? [Cu6] interconversion for polynuclear copper(I) complexes under controlled experimental settings is reported. It illustrates the key role of specific crystal growth conditions for accessing the target cluster nuclearity that consequently determines physical properties of the resulting solid state products. Thus, when copper(I) benzoate crystallizes from a 1, 2-dichlorobenzene solution at room temperature, it forms [Cu4]-core based crystalline material, [Cu4(O2CC6H5)4] (1). In contrast, crystal growth by deposition from the gas phase at elevated temperatures results in the exclusive formation of [Cu6(O2CC 6H5)6] (2). Complexes 1 and 2 have been isolated in pure form, fully characterized, and reversibly interconverted into each other. The effect of a core structure on the spectroscopic properties of 1 and 2, such as IR, Raman, and photoluminescence, has been investigated. Additionally, a combination of X-ray powder and single crystal diffraction methods has been used to discover the temperature induced phase transition in the hexanuclear copper(I) system. Two modifications of 2 exhibiting slightly different solid state packing of the [Cu6(O2CC 6H5)6] units have been identified at room and low temperature. Moreover, reversible single-crystal-to-singlecrystal transitions between these polymorphic forms have been confirmed. The important role of weak intermolecular interactions between polynuclear copper(I) units in the solid state has also been revealed and discussed.
Cu-Catalyzed C-H Alkenylation of Benzoic Acid and Acrylic Acid Derivatives with Vinyl Boronates
Li, Jian-Jun,Wang, Cheng-Gang,Yu, Jin-Feng,Wang, Peng,Wang, Peng,Yu, Jin-Quan
supporting information, p. 4692 - 4696 (2020/06/25)
An efficient Cu-catalyzed C-H alkenylation with acyclic and cyclic vinyl boronates was realized for the first time under mild conditions. The scope of the vinyl borons and the compatibility with functional groups including heterocycles are superior than Pd-catalyzed C-H coupling with vinyl borons, providing a reliable access to multisubstituted alkenes and dienes. Subsequent hydrogenation of the product from the internal vinyl borons will lead to installation of secondary alkyls.
Oxidation of substituted phenols using copper(II) metallatriangles formed through ligand sharing
Mahiya, Kuldeep,Kumar, Ravinder,Lloret, Francisco,Mathur, Pavan
, p. 663 - 668 (2014/07/22)
Reaction of N2,N2′-bis-[(1-butyl-benzimidazol- 2yl)methyl]biphenyl-2,2′-dicarboxamide (L) with CuX2nH 2O in methanol leads to the assembly of four trinuclear Cu(II) complexes with the general formula [Cu3(L)3X 3]3XnH2OmMeCN, where X = Cl-, Br-, NO3- and C6H5COO- and n = 0-5, m = 0-8 (compounds 1-4, respectively). The structure of one of the complex contains three Cu(II) metal ions at the corners of an equilateral triangle. Each of the copper(II) are coordinated through two benzimidazolyl imine N-atoms and two amide carbonyl O-atoms and the apical position is occupied by an anionic nitrate ion, leading to a distorted square pyramidal environment. The magnetic susceptibility data were analyzed through Hamiltonian H = -J (S 1S2 + S2S3 + S1S 3) obtaining -J = 0.16, 0.12, 0.15 and 0.14 cm-1 for 1-4, respectively. X-Band EPR spectra typically show a broad single line at 120 K with g ～ 2.11. Oxidation of phenols was studied homogeneously using copper(II) metallatriangles (1-3) as catalyst in acetonitrile. The oxidation of 2,4,6-tri-tert-butyl phenol yields the corresponding quinone after oxidative dealkylation. The oxidation of 2-amino-5-methyl phenol yields the corresponding phenoxazinone while the oxidation of 2-amino-4-tert-butyl phenol yields the phenoxazine instead of phenoxazinone. The products so obtained were analyzed by NMR and X-ray single crystallography.
RESIST COMPOSITION, METHOD OF FORMING RESIST PATTERN, NOVEL COMPOUND AND METHOD OF PRODUCING THE SAME, AND ACID GENERATOR
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, (2009/04/24)
A compound represented by formula (I); and a compound represented by formula (b1-1): wherein X represents —O—, —S—, —O—R3— or —S—R4—, wherein each of R3 and R4 independently represents an alkylene group of 1 to 5 carbon atoms; R2 represents an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, a halogenated alkyl group of 1 to 6 carbon atoms, a halogen atom, a hydroxyalkyl group of 1 to 6 carbon atoms, a hydroxyl group or a cyano group; a represents an integer of 0 to 2; Q1 represents an alkylene group of 1 to 12 carbon atoms or a single bond; Y1 represents an alkylene group of 1 to 4 carbon atoms or a fluorinated alkylene group; M+ represents an alkali metal ion; and A+ represents an organic cation.
Copper(I) carboxylates of type [(nBu3P) mCuO2CR] (m = 1, 2, 3) - Synthesis, properties, and their use as CVD precursors
Jakob, Alexander,Shen, Yingzhong,Waechtler, Thomas,Schulz, Stefan E.,Gessner, Thomas,Riedel, Ralf,Fasel, Claudia,Lang, Heinrich
, p. 2226 - 2234 (2009/05/08)
Copper(I) carboxylates of type [(nBu3P)mCuO 2CR] (m = 1: 3a, R = Me; 3b, R = CF3; 3c, R = Ph; 3d, R = CH=CHPh. m = 2: 4a, R = Me; 4b, R = CF3; 4c, R = Ph; 4d, R = CH= CHPh. m = 3: 8a, R = Me; 8b, R = CF3; 8c, R = CH2Ph; 8d, R = (CH 2OCH2)3H; 8e, R = cC 4H7O) are accessible by following synthesis methodologies: the reaction of [CuO2CR] (1a, R = Me; 1b, R = CF3; 1c, R = Ph; 1d, R = CH=CHPh) with m equivalents of nBu3P (2) (m = 1, 2, 3), or treatment of [(nBu3P)mCuCl] (5a, m = 1; 5b, m = 2) with [KO2CCF3] (6). A more straightforward synthesis method for 8a - 8e is the electrolysis of copper in presence of HO2CR (7a, R = Me; 7b, R = CF3; 7c, R = CH2Ph; 7d, R = (CH2OCH2)3H; 7e, R = cC 4H7O) and 2, respectively. This method allows to prepare the appropriate copper(I) carboxylate complexes in virtually quantitative yield, analytically pure form, and on an industrial scale. IR spectroscopic studies reveal that the carboxylic units in 4, 5, and 8 bind in a unidentate, chelating or μ-bridging fashion to copper(I) depending on m and R. The thermal properties of 4, 6, and 8 were determined by TG and DSC studies. Based on TG-MS experiments a conceivable mechanism for the thermally induced decomposition of these species is presented. Hot-wall Chemical Vapor Deposition experiments (CVD) with precursor 4b showed that copper could be deposited at 480°C onto a TiN-coated oxidized silicon substrate. The copper films were characterized by SEM and EDX studies. Pure layers were obtained with copper particles of size 200 - 780 nm.
Synthesis and characterization of new mono-, di-, and trinuclear copper(II) triethanolamine-carboxylate complexes
Escovar, Raphael M.,Thurston, John H.,Ould-Ely, Teyeb,Kumar, Arvind,Whitmire, Kenton H.
, p. 2867 - 2876 (2008/10/09)
A series of triethanolamine copper(II) carboxylate complexes have been synthesized and characterized both structurally and spectroscopically. The structures of the compounds and the nuclearity of the resulting coordination complexes are influenced both by the stoichiometry of the reagents and the steric and electronic influences of the anionic ligands present in the copper coordination spheres. The complexes can be prepared in high yields and purity as highly crystalline solids. Herein we report the spectroscopic and structural data for [NaCu(CF3COO)3(TEAH3)] (1), [Cu(C 6H5COO)(TEAH2)]2·2H 2O (2), [Cu3(CH3COO)4(TEAH 2)2] (3), [Cu3(HCOO)4(TEAH 2)2] (4) and [Cu3(CF3OO) 2(TEAH2)2-(CH3OH) 2][CF3CO2]2 (5) (TEAH3 = triethanolamine (N(CH2CH2OH)3); [TEAH 2]- = mono-deprotonated ion; [TEAH]2- = doubly deprotonated ion). Two approaches to these compounds were employed:direct reaction of copper(II) carboxylates with TEAH3 and reaction of the tetrameric compound [{Cu(TEAH)}4] (6) with copper(II) carboxylates. Compound 1 is polymeric in the solid state, being a double salt of sodium trifluoroacetate and (triethanolamine)copper(II) trifluoroacetate, while 2 exists as a simple dimer. Compounds 3, 4 and 5 are trinuclear complexes with Cu3 chains connected by bridging carboxylate and triethanolamine ligands. 3 was characterized as three crystal modifications: an unsolvated form and as a methanol solvate 3.2MeOH that was found to exist in both monoclinic and orthorhombic forms. 4 was also found to exist as a methanol solvate, 4.1.70 MeOH. 5 shows coordination isomerism compared to compounds 3 and 4 in that two of the carboxylate ligands in the metal coordination spheres on the end copper atoms have been replaced by solvent methanol. The magnetic behavior of the di- and trinuclear species has been probed and reveals that at low temperatures the metal centers exhibit strong ferromagnetic coupling, which, on warming, switches to simple paramagnetic behavior.
Novel (η2-Alkyne)copper(I) Carboxylate Complexes
Lang, Heinrich,Koehler, Katrin,Zsolnai, Laszlo
, p. 519 - 524 (2007/10/02)
The reaction of Me3SiCCSiMe3 (1) with copper(I) carboxylates (2a: R = Me; 2b: R = Ph) yields the tetranuclear compounds 2-Me3SiCCSiMe3)2>2 (3a: R = Me; 3b: R = Ph) and dimeric 2-Me3SiCCSiMe3)>2 (6a: R = Me; 6b: R = Ph).Compounds 6a and 6b could only be characterized by using IR and NMR techniques, since in solution these compounds eliminate 1 to afford 3a or 3b, respectively.Complexes 3a and 3b can additionally be synthesized by the reaction of 2-Me3SiCCSiMe3)CuBr>2 (4) with (5a: R = Me; 5b: R = Ph).In 6 two carboxylate moieties are μ-bridging two (η2-Me3SiCCSiMe3)Cu building blocks, and the Me3SiCCSiMe3 fragments are each η2-coordinated to one copper atom.In 3 the Me3SiCCSiMe3 units are each η2-coordinated to two copper atoms and are perpendicularly orientated to the copper(I) core; the four copper atoms form a square-planar arrangement.Compounds 3a and 3b have been characterized by analytical and spectroscopic data (IR, 1H-, 13C-NMR, MS) and 3a by X-ray-analysis. - Key Words: Copper(I) complexes / Carboxylates / Alkynes
Synthesis, Structural Characterisation and Studies of Octanuclear Copper Complexes of Pyridonate and Carboxylate Ligands
Blake, Alexander J.,Grant, Craig M.,Gregory, Christopher I.,Parsons, Simon,Rawson, Jeremy M.,et al.
, p. 163 - 176 (2007/10/02)
A series of octanuclear copper(II) complexes has been prepared which features carboxylate and 2-pyridonate ligands.These compounds have the general formula (where R = Me, Ph or CF3, and L = 6-chloro-, 6-bromo- or 6-methyl-2-pyridonate).X-Ray structural analyses of the acetate complexes indicate that the compounds contain an edge-sharing Cu6O2 bitetrahedral core, surrounded by two units.The Cu...Cu contacts within the core vary from 2.92 to 3.58 Angstroem, depending on the ligand bridging the metal-metal vector.Two routes to these complexes have been investigated, one involving reaction of preformed copper pyridonate complexes with copper carboxylates, the second involving reaction of copper carboxylates with molten HL.Differential scanning calorimetry and thermogravimetric analysis studies of the latter route show it proceeds via formation of copper pyridonate complexes.The FAB mass spectral results show interesting fragmentation patterns, consistent with the observed structures, and NMR spectra of the octanuclear complexes show paramagnetically shifted resonances due to both the pyridonate and carboxylate ligands.Magnetic studies of (L = 6-chloro- or 6-bromo-2-pyridonate) show largely antiferromagnetic exchange coupling within the Cu6O2 core.The structure of the complexes and the magnitude of the couplings lead to spin-frustrated systems, with subtle differences between the two complexes studied.
THE DIRECT ELECTROCHEMICAL SYNTHESIS OF SOME TRANSITION METAL CARBOXYLATES
Kumar, N.,Tuck, Dennis G.,Watson, Katherine D.
, p. 740 - 743 (2007/10/02)
The transition metal carboxylates M(O2CR)n (M=Cr, R=C2H5, C6H5, n=3; M=Mn, Fe, Ni, R=CH3, C2H5, C6H5, n-C7H15, n=2, not all combinations) have been prepared by oxidising suitable metal anodes electrochemically in solutions of RCOOH in acetonitrile.With Co and Cu, a wide range of carboxylic acids (R=C2H5, c-C3H5, c-C5H9, C6H5, n-C4H9, n-C7H15, 2-ethylhexanoic, oleic, linoleic) has been used succesfully to give M(O2CR)2.The advantages of the method are discussed.The preparation of Cu(O2CR)2 involves the prior formation of CuO2CR at the anode, followed by oxidation by the solvent.
