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1.
A novel C-S bond formation reaction took place, when a lithium phenolate derivative was treated with a disulfide-bridged dicopper(I) complex or a bis(micro-thiolato)dicopper(II) complex under very mild conditions. The reaction has been suggested to proceed via a disulfide-bridged (micro-phenoxo)dicopper(I) complex as the common reaction intermediate. Copper(II) complexes of the modified ligands containing a thioether group (products of the C-S bond formation reaction) have been isolated and structurally characterized by X-ray analysis as model compounds of the active site of galactose oxidase. Mechanism of the C-S bond formation reaction is also discussed in relation to the biosynthetic mechanism of the organic cofactor Tyr-Cys of galactose oxidase. 相似文献
2.
An unprecedented clean interconversion between a novel bis(mu-thiolato)dicopper(II) complex (1) and a disulfide-bridged dicopper(I) complex (3) through a disulfide-bridged (mu-chloro)dicopper(I) complex (2) mediated by chloride ion has been established for the first time, providing a new redox chemistry of the transition metal-sulfur complexes. Crystal structures of 1 and 3 as well as spectroscopic features of the compounds are reported. 相似文献
3.
Solid complex compounds of Fe(II) and Fe(III) ions with rutin were obtained. On the basis of the elementary analysis and thermogravimetric
investigation, the following composition of the compounds was determined: (1) FeOH(C27H29O16)·5H2O, (2) Fe2OH(C27H27O16)·9H2O, (3) Fe(OH)2(C27H29O16)·8H2O, (4) [Fe6(OH)2(4H2O)(C15H7O12)SO4]·10H2O. The coordination site in a rutin molecule was established on the basis of spectroscopic data (UV–Vis and IR). It was supposed
that rutin was bound to the iron ions via 4C=O and 5C—oxygen in the case of (1) and (3). Groups 5C–OH and 4C=O as well as 3′C–OH and 4′C–OH of the ligand participate in binding metals ions in the case of (2). At an excess of iron(III) ions with regard to rutin under the synthesis conditions of (4), a side reaction of ligand oxidation occurs. In this compound, the ligands’ role plays a quinone which arose after rutin
oxidation and the substitution of Fe(II) and Fe(III) ions takes place in 4C=O, 5C–OH as well as 4′C–OH, 3′C–OH ligands groups.
The magnetic measurements indicated that (1) and (3) are high-spin complexes. 相似文献
4.
Duan Chung-ying Lu Zhong-lin You Xiao-zeng Mak Thomas C. W. 《Transition Metal Chemistry》1997,23(1):77-79
A novel, high-symmetry dicopper complex bridged by only a single hydroxo has been synthesized and structurally characterized.
The coordination geometry of copper(II) is a strict trigonal bipyramidal of C3 symmetry. The three equivalent amino nitrogen
atoms of the ligand form the equatorial plane, while the tripodal nitrogen atom and the hydroxo anion occupy axial positions.
The bridging Cu-(OH)-Cu angle of the single hydroxo anion is only 136.5°, which does not agree well with data found in similar
compounds. The magnetic–structural relation is discussed.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
5.
Thahira B. S. A. Ravoof Karen A. Crouse M. Ibrahim M. Tahir Fiona N. F. How Rozita Rosli David J. Watkins 《Transition Metal Chemistry》2010,35(7):871-876
A tridentate nitrogen-sulfur Schiff base, 3-methylbenzyl 2-(6-methylpyridin-2-ylmethylene)hydrazine carbodithioate (6mpyS3M),
was synthesized by condensation of 6-methylpyridine-2-aldehyde with S-3-methylbenzyldithiocarbazate. It crystallized in space
group P 21/n. It displayed intermolecular N–H···N hydrogen bonding between the α-nitrogen and the pyridyl nitrogen. The thione sulfur is in a trans position with respect to the 6-methylpyridine fragment across the C–N bond but adopts a cis position with the 3-methylbenzyl fragment through the C–S bond. Octahedral complexes containing two 6mpyS3M ligands were
prepared with Cu(II), Ni(II), Zn(II) and Cd(II). 6mpyS3M and its metal complexes were assayed against selected microbes and
two breast cancer cell lines. 6mpyS3M was strongly active against both cancer cell lines. Its metal complexes showed high
selectivity with Cu(II), Ni(II) and Zn(II) complexes strongly active against only one of the cancer cell lines, whereas the
Cd(II) complex was strongly active only against the other. Only Cu(II) and Cd(II) complexes were active against some of the
bacteria. 相似文献
6.
Michito Shiotsuka Naoki Nishiko Yasushi Tsuji Noboru Kitamura Satoru Onaka Katsuya Sako 《Transition Metal Chemistry》2010,35(2):129-135
A novel asymmetric dinuclear gold(I) complex with 3,6-diethynylphenanthroline, 3,6-bis{(PPh3)–Au–C≡C}2-phen, has been synthesized from Au(PPh3)Cl (PPh3 = triphenylphosphine) and 3,6-diethynyl-1,10-phenanthroline. The asymmetrical dinuclear gold(I) complex, 3,6-bis{(PPh3)–Au–C≡C}2-phen, demonstrated a weak phosphorescence assignable to the metal-perturbed 3
π–π* transition in the long wavelength region compared to an intense emission of the symmetrical dinuclear complex with 3,8-diethynylphenanthroline,
3,8-bis{(PPh3)–Au–C≡C}2-phen. A similar tendency of phosphorescent bands for the mononuclear gold(I) complexes with 5-ethynylphenanthroline, 5-{(PPh3)–Au–C≡C}-phen, and 3-ethynylphenanthroline, 3-{(PPh3)–Au–C≡C}-phen was observed. The absorption bands assignable to the π–π*(C≡Cphen) transition and phosphorescent emission assignable to the metal-perturbed 3
π–π* transition for these four gold(I) complexes were reasonably consistent with the results calculated by DFT and TD-DFT. 相似文献
7.
Twelve-, fifteen-, and eighteen-membered diaza-crown-N, N-′dialkanoic acids LH2 and their inner salt copper(II) complexes CuL and dicopper complex [CuL(3). CuCl2. CH3OHn were obtained. The complexes of 15- and 18-membered ligands contain Cu2+ ion inside the ring. 相似文献
8.
J Ferrando-Soria M Castellano R Ruiz-García J Cano M Julve F Lloret J Pasán C Ruiz-Pérez L Cañadillas-Delgado Y Li Y Journaux E Pardo 《Chemical communications (Cambridge, England)》2012,48(67):8401-8403
A unique magnetic electroswitching behavior has been observed in an oxamato-based permethylated dicopper(II) paracyclophane; upon reversible one-electron oxidation of the double tetramethyl-substituted p-phenylenediamidate bridging skeleton, the spin alignment of the two Cu(II) ions (S(Cu) = ?) changes from antiparallel (OFF) to parallel (ON) in the resulting dicopper(II) π-radical cation species. 相似文献
9.
Battaini G Monzani E Perotti A Para C Casella L Santagostini L Gullotti M Dillinger R Näther C Tuczek F 《Journal of the American Chemical Society》2003,125(14):4185-4198
The dicopper(II) complex [Cu(2)(L)](4+) (L = alpha,alpha'-bis[bis[2-(1'-methyl-2'-benzimidazolyl)ethyl]amino]-m-xylene) reacts with hydrogen peroxide to give the dicopper(II)-hydroquinone complex in which the xylyl ring of the ligand has undergone a double hydroxylation reaction at ring positions 2 and 5. The dihydroxylated ligand 2,6-bis([bis[2-(3-methyl-1H-benzimidazol-2-yl)ethyl]amino]methyl)benzene-1,4-diol was isolated by decomposition of the product complex. The incorporation of two oxygen atoms from H(2)O(2) into the ligand was confirmed by isotope labeling studies using H(2)(18)O(2). The pathway of the unusual double hydroxylation was investigated by preparing the two isomeric phenolic derivatives of L, namely 3,5-bis([bis[2-(1-methyl-1H-benzimidazol-2-yl)ethyl]amino]methyl)phenol (6) and 2,6-bis([bis[2-(1-methyl-1H-benzimidazol-2-yl)ethyl]amino]methyl)phenol (7), carrying the hydroxyl group in one of the two positions where L is hydroxylated. The dicopper(II) complexes prepared with the new ligands 6 and 7 and containing bridging micro-phenoxo moieties are inactive in the hydroxylation. Though, the dicopper(II) complex 3 derived from 6 and containing a protonated phenol is rapidly hydroxylated by H(2)O(2) and represents the first product formed in the hydroxylation of [Cu(2)(L)](4+). Kinetic studies performed on the reactions of [Cu(2)(L)](4+) and 3 with H(2)O(2) show that the second hydroxylation is faster than the first one at room temperature (0.13 +/- 0.05 s(-1) vs 5.0(+/-0.1) x 10(-3) s(-1)) and both are intramolecular processes. However, the two reactions exhibit different activation parameters (Delta H++ = 39.1 +/- 0.9 kJ mol(-1) and Delta S++ = -115.7 +/- 2.4 J K(-1) mol(-1) for the first hydroxylation; Delta H++ = 77.8 +/- 1.6 kJ mol(-1) and Delta S++ = -14.0 +/- 0.4 J K(-1) mol(-1) for the second hydroxylation). By studying the reaction between [Cu(2)(L)](4+) and H(2)O(2) at low temperature, we were able to characterize the intermediate eta(1):eta(1)-hydroperoxodicopper(II) adduct active in the first hydroxylation step, [Cu(2)(L)(OOH)](3+) [lambda(max) = 342 (epsilon 12,000), 444 (epsilon 1200), and 610 nm (epsilon 800 M(-1)cm(-1)); broad EPR signal in frozen solution indicative of magnetically coupled Cu(II) centers]. 相似文献
10.
The synthesis of dicopper(I) complexes [Cu2(BBAN)(MeCN)2](OTf)2 (1), [Cu2(BBAN)(py)2](OTf)2 (2), [Cu2(BBAN)(1-Me-BzIm)2](OTf)2 (3), [Cu2(BBAN)(1-Me-Im)2](OTf)2 (4), and [Cu2(BBAN)(mu-O2CCPh3)](OTf) (5), where BBAN = 2,7-bis((dibenzylamino)methyl)-1,8-naphthyridine, py = pyridine, 1-Me-Im = 1-methylimidazole, and 1-Me-BzIm = 1-methylbenzimidazole, are described. Short copper-copper distances ranging from 2.6151(6) to 2.7325(5) A were observed in the solid-state structures of these complexes depending on the terminal ligands used. The cyclic voltammogram of compound 5 dissolved in THF exhibited a reversible redox wave at E1/2 = -25 mV vs Cp2Fe+/Cp2Fe. When complex 5 was treated with 1 equiv of silver(I) triflate, a mixed-valence dicopper(I,II) complex [Cu2(BBAN)(mu-O2CCPh3)(OTf)](OTf) (6) was prepared. A short copper-copper distance of 2.4493(14) A observed from the solid-state structure indicates the presence of a copper-copper interaction. Variable-temperature EPR studies showed that complex 6 has a fully delocalized electronic structure in frozen 2-methyltetrahydrofuran solution down to liquid helium temperature. The presence of anionic ligands seems to be an important factor to stabilize the mixed-valence dicopper(I,II) state. Compounds 1-4 with neutral nitrogen-donor terminal ligands cannot be oxidized to the mixed-valence analogues either chemically or electrochemically. 相似文献
11.
A series of calcium silicate hydrate (C–S–H)-polymer nanocomposite
(C–S–HPN) materials were prepared by incorporating poly(acrylic
acid) (PAA) into the inorganic layers of C–S–H during precipitation
of quasicrystalline C–S–H from aqueous solution. The as-synthesized
C–S–HPN materials were characterized by X-ray fluorescence (XRF),
X-ray diffraction (XRD), scanning electron microscopy-energy dispersive spectroscopy
(SEM-EDS), Fourier-transform infrared (FTIR) spectroscopy, thermogravimetric
analysis (TG) and differential scanning calorimetry (DSC). The XRD analysis
of C–S–HPN materials suggest the intermediate organizations presenting
intercalation of PAA within C–S–H and exfoliation of C–S–H.
The SEM micrographs of C–S–H, PAA and C–S–HPN materials
with different PAA contents exhibit the significant differences in their morphologies.
The effect of the material’s composition on the thermal stability of
a series of C–S–HPN materials along with PAA and C–S–H
were studied by TG, DTA and DSC. Three significant decomposition temperature
ranges were observed on the TG curves of all C–S–HPN materials. 相似文献
12.
The conformational composition of gaseous MTMNB and the molecular structures of the rotational forms have been studied by
electron diffraction at 130∘C aided by results from ab initio and density functional theory calculations. The conformational potential energy surface
has been investigated by using the B3LYP/6-31G(d,p) method. As a result, six minimum-energy conformers have been identified.
Geometries of all conformers were optimized using MP2/6-31G(d,p), B3LYP/6-31G(d,p), and B3LYP/cc-pVTZ methods. These calculations
resulted in accurate geometries, relative energies, and harmonic vibrational frequencies for all conformers. The B3LYP/cc-pVTZ
energies were then used to calculate the Boltzmann distribution of conformers. The best fit of the electron diffraction data
to calculated values was obtained for the six conformer model, in agreement with the theoretical predictions. Average parameter
values (ra in angstroms, angle α in degrees, and estimated total errors given in parentheses) weighted for the mixture of six conformers
are r(C–C) = 1.507(5), r(C–C)ring, av = 1.397(3), r(C–S)av = 1.814(4), r(C–N) = 1.495(4), r(N–O)av = 1.223(3), ∠(C–C–C)ring = 116.0–122.5, ∠ C6–C4–C7 = 118.2(4), ∠ C–C–S = 113.6(6), ∠ C–S–C = 98.5(12), ∠ N–C–C4 = 121.9(3), ∠(O–N–C)av = 116.8(3), ∠ O–N–O = 127.0(4). Torsional angles could not be refined. Theoretical B3LYP/cc-pVTZ torsional angles for the
rotation about C–N bond, φC−N, were found to be 30.5–36.5∘ for different conformers. As to internal rotation about C–C and C–S bonds, values of φC−C = 68–118∘ and φC−S = 66–71∘ were obtained for the three most stable conformers with gauche orientation with respect to these bonds.
Some conclusions of this work were presented in a short communication in Russ. J. Phys. Chem. 2005, 79, 1701. 相似文献
13.
《Liquid crystals》1997,23(3):313-315
The synthesis of a series of bidentate Schiff 's bases; 3,5-bis(3 ,4 ,5-trialkoxybenzyloxy)phenyl2- N -(3-hydroxypropy)iminopropyl ketone, and their dicopper complexes are reported. The liquid crystalline behaviour of these dicopper complexes was studied by DSC, polarized optical microscopy and X-ray diffraction. The phases were characterized and identified as hexagonal columnar (D ) phases, which are typical of disc-like molecules. h 相似文献
14.
Mahmut Ulusoy Hasan Karabıyık Rafet Kılınçarslan Muhittin Aygün Bekir Çetinkaya Santiago García-Granda 《Structural chemistry》2008,19(5):749-755
Copper(II) and cobalt(II) complexes of salicylaldimine obtained by the condensation of N,N-diethyl-2-methyl-1,4-phenylenediamine with 3,5-di-tert-butyl-2-hydroxybenzaldehyde have been synthesized and characterized by elemental analyses, magnetic susceptibility measurements,
cyclic voltammetry, and FT-IR and UV–Vis spectroscopy. The molecular structure of the title copper(II) complex was determined
by the single crystal X-ray diffraction technique. The Cu(II) center is coordinated by four atoms of the donor set in a compressed
tetrahedral trans-[N2O2] environment, which can be essentially ascribed to the presence of bulky fragments of the ligand. The computed bond valences
of the copper verify +2 oxidation state and indicate that the copper bonds, in particular Cu–N bonds, are elongated due to
steric effects from bulky substituents in the ligands, N-(4-diethylamino-2-methylphenyl). Intermolecular C–H···π interactions leading to centrosymmetric synthons serve to stabilize
periodic organization of the molecules. 相似文献
15.
Syntheses, structures, and magnetic properties of two heterobridged mu-alkoxo-mu-7-azaindolate dicopper(II) complexes, [Cu(II)2(L-F)(mu-C7H5N2)] (1) and [Cu(II)2(L-H)(mu-C7H5N2)].CH3OH (2) (H3L-F = 1,3-bis(3-fluorosalicylideneamino)-2-propanol; H3L-H = 1,3-bis(salicylideneamino)-2-propanol) have been reported. Aside from being a new type of heterobridged complex, 1 and 2 exhibit ferromagnetic interaction (2J = 52 cm(-1) for 1 and 33.4 cm(-1) for 2) despite orbital complementarity (7-azaindolate HOMO is antisymmetric). 相似文献
16.
L. I. Zakharkin V. A. Ol'shevskaya R. P. Evstigneeva V. N. Luzgina L. E. Vinogradova P. V. Petrovskii 《Russian Chemical Bulletin》1998,47(2):340-342
5,10,15,20-Tetra[3-(o- andm-carboranyl)butyl]porphyrins containing carborane groups bonded to alkyl substituents of the porphyrin cycle by the C−B σ-bond
were obtained by condensation of 4-(o- andm-carboran-9-yl)pentanals with pyrrole.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 347–349, February, 1998. 相似文献
17.
Brown EC Aboelella NW Reynolds AM Aullón G Alvarez S Tolman WB 《Inorganic chemistry》2004,43(11):3335-3337
Rare examples of (mu-eta2:eta2-disulfido)dicopper complexes have been prepared from Cu(I) and Cu(II) complexes of beta-diketiminate and anilido-imine supporting ligands. A novel byproduct derived from sulfur functionalization of the methine position of a beta-diketiminate ligand was identified. DFT calculations on [(LCu)2X2] (L = beta-diketiminate, X = O or S) complexes rationalize the absence of a bis(mu-sulfido)dicopper isomer, [Cu2(mu-S)2](2+), in the synthetic reactions, yet predict that a [Cu2(mu-S)2](0) core is a stable product of 2-electron reduction of the [Cu2(mu-eta2:eta2-S2)](2+) unit. Exchange of the disulfido ligand was discovered upon reaction of a (mu-eta2:eta2-disulfido)dicopper complex with a Cu(I) reagent. 相似文献
18.
The triethanolamine complexes, [M(tea)2]sq·nH2O, (n=2 for Co(II), n=0 for Ni(II), Cu(II) and n=1 for Cd(II), tea=triethanolamine, sq2−=squarate), have been synthesized and characterized by elemental analyses, magnetic susceptibility and conductivity measurements,
UV-Vis and IR spectra, and thermal analyses techniques (TG, DTG and DTA). The Co(II), Ni(II) and Cu(II) complexes possess
octahedral geometry, while the Cd(II) complex is monocapped trigonal prismatic geometry. Dianionic squarate behaves as a counter
ion in the complexes. The thermal decomposition of these complexes takes place in three stages: (i) dehydration, (ii) release of the tea ligands and (iii) burning of organic residue. On the basis of the first DTGmax of the decomposition, the thermal stability of the anhydrous complexes follows the order: Ni(II), 289°C>Co(II), 230°C>Cu(II),
226°C>Cu(II), 170°C in static air atmosphere. The final decomposition products — the respective metal oxides — were identified
by FTIR spectroscopy. 相似文献
19.
Tomislav Fri
i Alan J. Lough George Ferguson Branko Kaitner 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(5):m313-m315
The title dimeric complex, bis{μ‐2,2′‐[hexane‐1,6‐diylbis(nitrilomethylidyne)]diphenolato‐1:2κ4O,N:N′,O′}dicopper(II),[Cu2(C20H22N2O2)2], has been investigated by single‐crystal X‐ray diffraction, by thermogravimetric analysis and differential scanning calorimetry, and also by FT–IR spectroscopy. Different synthetic and crystallization procedures gave crystals which were quite different in appearance, and it was initially thought that these were different polymorphic forms. Subsequent structure determination showed, in fact, serendipitous preparation of crystals in the P41 space group by one method and in space group P43 by the other. In these enantiomorphic structures, the Cu atoms have a distorted flattened tetrahedral coordination, with Cu—N and Cu—O distances in the ranges 1.954 (4)–1.983 (4) and 1.887 (4)–1.903 (4) Å, respectively. 相似文献