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1.
V. F. Shul’gin E. A. Sarnit O. V. Konnik E. B. Rusanov A. S. Bogomyakov V. I. Ovcharenko V. V. Minin 《Russian Journal of Coordination Chemistry》2012,38(1):44-49
The structures and results of the static magnetic susceptibility investigation of the copper(II) binuclear complex with salicylic
acid diacyl hydrazide (H2L), [Cu2(L)(Py)4] (I), and the copper(II) trinuclear complex with diacyl dihydrazide of salicylic and glutaric acids (H6L′), [Cu3(L′)(Py)4] · 2Py (II), are described. The exchange antiferromagnetic interactions between the paramagnetic centers with the exchange interaction
parameter −2J = 119 cm−1 for dimer I and 14 cm−1 for trinuclear complex II are detected. 相似文献
2.
A novel heterospin one-dimensional (1-D) chain complex containing both Cu(II) and nitroxide radical ligands, {[Cu(tcph)(H2O)4][Cu(tcph)(NIT3Py)2]·2H2O}
n
(1) (H2tcph = tetrachloro-phthalic acid, NIT3Py = 2-(3′-pyridyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide), has been synthesized
and structurally characterized. The structure consists of neutral chains of copper(II) ions bridged by tcph and coordinated
alternatively by nitroxide radicals as spin branches and solvated water as co-ligand. The magnetic data were fitted using
an approximate theoretical model based on population analysis to obtain the coupling parameter values of J
Cu2-Rad = 22.4 cm−1 and J′Cu1-Cu2 = −2.4 cm−1, indicating the intramolecular ferromagnetic interaction between Cu(II) and NIT3Py and weak antiferromagnetic interaction
between Cu1 and Cu2 linked by tcph. 相似文献
3.
A novel Salen-type bisoxime ligand, 6,6′-dimethoxy-2,2′-[(1,4-butylene)dioxybis(nitrilomethylidyne)]diphenol (H2L) and its tetranuclear Cu(II) complex, [Cu4L2(pic)4(H2O)2]·2H2O, have been synthesized and characterized by elemental analyses, IR, TG-DTA and 1H-NMR etc. The X-ray crystal structure of the complex reveals that formation of a tetranuclear structure, which consists of four copper(II)
atoms, two pentadentate L2−units, four picratols, two coordinated water molecules and two crystallizing water molecules. Around four copper ions are
all octahedral geometries. It was demonstrated that the picratols in the tetranuclear copper(II) complex show a novel tridentate
coordination mode. 相似文献
4.
The present work illustrates the versatile coordination modes of the amide-based ligands towards copper(II) ion. The reaction of the deprotonated form of the ligand, [L1]2− with CuCl2 affords a linear trinuclear complex, [Cu3(L1)2(Cl)2(H2O)] (1) which has been characterized thoroughly including single crystal structure analysis. The structure of 1 shows that one of the arm of the flexible ligand flips to coordinate second copper(II) centre, resulting in the formation of a trinuclear complex. On the other hand, ligand H2L2 in its deprotonated form reacts with Cu(II) ion to give complex 2 with general formula, [Cu(L2)]n (2). The crystal structure of the complex 2 shows that each copper is square-pyramidal with 5th coordination coming from the O-atom of the amide group from a neighbouring complex. This results in the generation of an one-dimensional zig-zag chain. The variable temperature magnetic measurements of the complexes, 1 and 2 show that while Cu ions in the former are antiferromagnetically coupled (J = −110.34 cm−1), a weak ferromagnetic interaction (J = +3.08 cm−1) exists in the later. A rationale, based on the orbital overlap from the copper ions and associated ligands, is provided for the observed magnetic coupling between the copper ions. 相似文献
5.
A new type of two-dimensional network was found in the hydrogen-bonded molecular assemblies of copper(II) α,β-unsaturated
carboxylate complexes with TMP [OP(OMe)3], {Cu2A4(H2O)2[OP(OMe)3]}
n
[(1) A = CH2=CHCO2
−; (2) A = CH2=C(Me)CO2
−]. The crystal structure of (1) has been determined by single-crystal X-ray diffraction. Both complexes are unique in terms of a sheet structure brought
about by O—H ⋯ O hydrogen-bonded interactions both between neighbouring Cu2A4(H2O)2 units and between Cu2A4(H2O)2 and OP(OMe)3 molecules. The electronic reflectance spectra in the solid state suggest a square pyramidal coordination environment around
the copper(II) atom. Room temperature X-band e.s.r. spectra of powered samples and variable-temperature magnetic susceptibility
studies indicate the presence of strong antiferromagnetic exchange interactions between two copper(II) atoms, with 2J = −310 cm−1 for (1) and 2J = −304 cm−1 for (2) respectively.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
6.
Nine new μ-oxamido-bridged copper(II)-lanthanide(III)-copper(II) heterotrinuclear complexes described by the overall formula
Cu2(dmoxae)2Ln(NO3)3 {Ln = Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er; dmoxae = N,N′-bis[2-(dimethylamino)ethyl]oxamido dianions} have been synthesized by the strategy of ‘complex as ligand’, and characterized
by elemental analyses, molar conductivity measurements, i.r. and electronic spectral studies. The variable-temperature susceptibility
(2–300 K), e.s.r. measurements, and studies of the Cu2(dmoxae)2Gd(NO3)3 complex have revealed that the central gadolinium(III) and terminal copper(II) ions are ferromagnetically coupled with the
exchange integral J(Cu-Gd) = +2.1 cm−1, while an antiferromagnetic coupling is detected between the terminal copper(II) ions with J′(Cu-Cu)=−0.36 cm−1, on the basis of the spin Hamiltonian operator
.
A plausible mechanism for the ferromagnetic coupling between copper(II) and gadolinium(III) is discussed in terms of spin
polarization. 相似文献
7.
Wang Shi-bin Yang Guang-ming Yu Li-hua Wang Qing-lun Liao Dai-zheng 《Transition Metal Chemistry》2003,28(6):632-634
A dinuclear copper(II) [(LCu)(MeOH)Cu(phen)(MeOH)]ClO4·NO3 macrocyclic complex (where H2L = 2,3-dioxo-5,6:15,16-dibenzo-1,4,8,13-tetraazacyclo-pentadeca-7,13-diene; phen = 1,10-phenanthroline) has been synthesized and characterized by means of elemental analysis and its i.r. spectrum. Its crystal structure has been determined by single-crystal X-ray diffraction. In the complex, both the copper ions are penta-coordinated and have a distorted square pyramid configuration. Magnetic susceptibility measurements show antiferromagnetic exchange interactions (J = –207.64 cm–1) between the copper(II) ions. 相似文献
8.
Chun Yang Gongfeng Xu Bin Liu Qinglun Wang Daizheng Liao 《Frontiers of Chemistry in China》2008,3(3):294-297
The bimetallic complex of Ni2Co(TTHA)·12H2O (TTHA = triethylene tetraminehexaacetic acid) was synthesized and characterized structurally and magnetically. The title
complex crystallizes in the triclinic space group P ī with a = 0.7316(2), b = 0.8624(2), c = 1.5041(4) nm; α = 73.38(2), β = 83.97(2), γ = 70.50(2)°. The crystal structure is built up of [Ni2(TTHA)(H2O)2]2−, Co(H2O)62+ and water molecules. The variable magnetic measurement shows that there is strong antiferromagnetic interaction between two
Ni(II) ions in [Ni2(TTHA) (H2O)2]2− with J
Ni−Ni = −141.64 cm−1, g
Ni = 2.21 and that the constant of spin-orbit coupling of Co(II) ion is −134.8 cm−1.
__________
Translated from Acta Scientiarum Naturalium Universitatis Nankaiensis, 2007, 40(1): 6–10 [译自: 南开大学学报(自然科学版)] 相似文献
9.
Jing-Min Shi Feng-Xia Zhang Chang-Ju Wu Lian-Dong Liu Long Yi 《Transition Metal Chemistry》2006,31(7):879-881
A novel one-dimensional coordination polymer [Cu(μ
1,6-dmpzdo)(dmpzdo)2]·(ClO4)2 (dmpzdo = 2,5-dimethylpyrazine-1,4-dioxide) has been synthesized and its crystal structure determined by X-ray crystallography.
In the complex each Cu1 atom is located in a square planar coordination environment with two oxygen atoms O2 and O2A from
two dmpzdo terminal ligands, and two other oxygen atoms O3 and O3A from two μ
1,6-dmpzdo bridging ligands. The one-dimensional chain is constructed by the coordination of a μ
1,6-dmpzdo bridging ligand and Cu(II) ions. The data of the variable temperature (4–300 K) magnetic susceptibilities were fitted
by using the one-dimensional chain fitting formula, which gave the magnetic coupling constants 2J = −98.88 cm−1. 相似文献
10.
合成并结构表征了一种新型的线性三核锌(II)配合物,{[ZnL(OAc)]2Zn}∙CH3COCH3(H2L:乙二氧双(5-溴-2-羟基苯亚甲基胺))。X-射线结构表明配合物中三个锌(II)离子配位到了两个四齿的L2-单元和两个桥联的的乙酸根基团。围绕两端的Zn(1) 或 Zn(1)#1原子形成了扭曲的四方锥配位几何体,围绕中心Zn(2) 原子构成了一个稍微扭曲的八面体配位结构。同时,观察到锌(II)配合物能发出蓝绿色荧光,其最大发射波长为464 nm。 相似文献
11.
Galactose oxidase (GOase) is a fungal enzyme which is unusual among metalloenzymes in appearing to catalyse the two electron
oxidation of primary alcohols to aldehydes and H2O2. The crystal structure of the enzyme reveals that the coordination geometry of mononuclear copper(II) ion is square pyramidal,
with two histidine imidazoles, a tyrosinate, and either H2O (pH 7.0) or acetate (from buffer,pH 4-5) in the equatorial sites and a tyrosinate ligand weakly bound in the axial position. This paper summarizes the results
of our studies on the structure, spectral and redox properties of certain novel models for the active site of the inactive
form of GOase. The monophenolato Cu(II) complexes of the type [Cu(L1)X][H(L1) = 2-(bis(pyrid-2-ylmethyl)aminomethyl)-4-nitrophenol and X− = Cl−
1, NCS−
2, CH3COO−
3, ClO4
−
4] reveal a distorted square pyramidal geometry around Cu(II) with an unusual axial coordination of phenolate moiety. The coordination
geometry of 3 is reminiscent of the active site of GOase with an axial phenolate and equatorial CH3COO− ligands. All the present complexes exhibit several electronic and EPR spectral features which are also similar to the enzyme.
Further, to establish the structural and spectroscopic consequences of the coordination of two tyrosinates in GOase enzyme,
we studied the monomeric copper(II) complexes containing two phenolates and imidazole/pyridine donors as closer structural
models for GOase. N,N-dimethylethylenediamine and N,N’-dimethylethylenediamine have been used as starting materials to obtain
a variety of 2,4-disubstituted phenolate ligands. The X-ray crystal structures of the complexes [Cu(L5)(py)], (8) [H2(L5) = N,N-dimethyl-N’,N’-bis(2-hydroxy-4-nitrobenzyl) ethylenediamine, py = pyridine] and [Cu(L8)(H2O)] (11), [H2(L8) = N,N’-dimethyl-N,N’-bis(2-hydroxy-4-nitrobenzyl)ethylenediamine] reveal distorted square pyramidal geometries around Cu(II) with the axial tertiary
amine nitrogen and water coordination respectively. Interestingly, for the latter complex there are two different molecules
present in the same unit cell containing the methyl groups of the ethylenediamine fragmentcis to each other in one molecule andtrans to each other in the other. The ligand field and EPR spectra of the model complexes reveal square-based geometries even in
solution. The electrochemical and chemical means of generating novel radical species of the model complexes, analogous to
the active form of the enzyme is presently under investigation. 相似文献
12.
A new chelating radical ligand, IMMeBzIm (IMMeBzIm = 2-{2′-[(l′-methyl)benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl)
and its copper(II) complex [Cu(IMMeBzIm)2(ClO4)]·(ClO4) have been prepared and characterized by IR, magnetic and single-crystal X-ray analysis. In the crystal structures, both
free IMMeBzIm and the complex crystallize in monoclinic space groups P2(1)/c and C2/c, respectively. The structure of IMMeBzIm consists of mononuclear molecules. In the complex, the coordination geometry around
copper is a distorted square pyramid, and the apical position is occupied by one oxygen atom of ClO4
− anion. A 1-D polymer is formed through intermolecular H-bond interactions. The variable-temperature magnetic susceptibility
of the free IMMeBzIm suggests weak antiferromagnetic coupling with J = −1.12 cm−1 where the spin Hamitonian is defined as Ĥ = −2 JŜ
1
Ŝ
2
between radical and radical. 相似文献
13.
A new bimetallic cyano-bridged complex, based on copper(II) macrocycle and hexacyanoiron(III) as building blocks, [CuL(H2O)2]{[CuL][Fe(CN)6] · 2H2O} (1) (L = 1,3,6,8,11,14-hexaazatricyclo[12.2.1.18,11]-octadecane) has been synthesized and magnetically characterized. Make
a study of magnetic using a chain model which takes into account of monomeric impurity confirm showing an antiferromagnetic
coupling in paramagnetic ions with J = −0.170 cm−1 and 3.56 % impurity. 相似文献
14.
Qing-Lun Wang Xue-Qiao Jia Dai-Zheng Liao Shi-Ping Yan Peng Cheng Guang-Ming Yang Hong-Xia Ren Zong-Hui Jiang 《Transition Metal Chemistry》2006,31(4):434-440
A binuclear copper(II) complex with two symmetric end-on azido bridges: [Cu2(tacn)2(μ-N3)2](ClO4)2 · CH3OH (1), where tacn = 1,4,7-triazacyclononane, has been synthesized and structurally as well as magnetically characterized. Compound
(1) has the discrete binuclear structure, bridged by two end-on N3− anions. The macrocyclic ligand tacn functions as a terminal ligand. The magnetic data of compound (1) were analyzed by means of Ĥ = −2JŜ1Ŝ2 − DŜz, leading to J = 2.49 cm−1, g = 2.08, D = ±0.97 cm−1, zJ′ = −0.47 cm−1. The ferromagnetic interaction is discussed on the basis of the structural features and is compared with the model structure
of Ruiz. 相似文献
15.
Ming-Lai Fu Norma L. Rangel Richard D. Adams Jorge M. Seminario 《Journal of Cluster Science》2010,21(4):867-878
Abstract
Thiacalix[4]arenes are a unique family of polydentate ligands that offer a combination of four soft sulfur atoms together with four hard phenol oxygen atoms for binding to metal ions. In this study, the tetranuclear cadmium (II) complex Cd4II(tca)2·1.5CH2Cl2 (tca4− = tetra-anionic p-tert-butylthiacalix[4]arene) (1) was synthesized by reaction of a deprotonated p-tert-butylthiacalix[4]arene and various CdII salts. The structure of 1 was established by single crystal X-ray diffraction analysis. The neutral complex 1 contains a square arrangement of four cadmium (II) ions sandwiched between two tca4− ligands that have a ‘cone’ conformation similar to that of the free ligand. The absorption and emission properties of the free ligand H4tca and complex 1 have been recorded and explained by DFT calculations of the molecular orbitals and electronic transitions between them. 相似文献16.
Zhaoxiang Wu Francisco A. Fernandez-Lima Lisa M. Perez David H. Russell 《Journal of the American Society for Mass Spectrometry》2009,20(7):1263-1271
The dinuclear copper complex (α-cyano-4-hydroxycinnamic acid (CHCA) copper salt (CHCA)4Cu2), synthesized by reacting CHCA with copper oxide (CuO), yields increased abundances of [M + xCu − (x−1)H]+ (x = 1–6) ions when used as a matrix for matrix-assisted laser desorption ionization (355 nm Nd:YAG laser). The yield of
[M + xCu − (x−1)H]+ (x = 1∼6) ion is much greater than that obtained by mixing peptides with copper salts or directly depositing peptides onto
oxidized copper surfaces. The increased ion yields for [M + xCu − (x−1)H]+ facilitate studies of biologically important copper binding peptides. For example, using this matrix we have investigated
site-specific copper binding of several peptides using fragmentation chemistry of [M + Cu]+ and [M + 2Cu − H]+ ions. The fragmentation studies reveal interesting insight on Cu binding preferences for basic amino acids. Most notable
is the fact that the binding of a single Cu+ ion and two Cu+ ions are quite different, and these differences are explained in terms of intramolecular interactions of the peptide-Cu ionic
complex. 相似文献
17.
A new complex with the formula (NH4)4[Mo8O24(C3H2O2)2] · 4H2O (1) has been synthesized and characterized by single crystal X-ray diffraction and infrared spectrum. The complex is small yellow
crystal and space group P
1 with a = 9.9869(18) ?, b = 10.030(19) ?, c = 10.366(19) ?, α = 91.68(3)°, β = 98.94(3)°, γ = 119.37(2)°, V = 887(3) ?3, and Z = 1. The complex contains two malonic acid ligands bonded to the γ-Mo8
264− ions which consist of eight MoO6 edge-sharing octahedral. In this crystal structure, the octamolybdate anion is mutually hydrogen bonded by ammonium ions
and water molecules. 相似文献
18.
《Journal of Coordination Chemistry》2012,65(11):947-953
The trinuclear complex {[Cu(oxbe)(py)]2Ni(py)2}·2DMF has been prepared and characterized by elemental analysis, IR and electronic spectra and magnetic susceptibility, where H3oxbe is the dissymmetrical ligand N-benzoato-N′-(2-aminoethyl) oxamido, py?=?pyridine, DMF?=?dimethylformamide. The molecular structure of this complex is centrosymmetrical and has an extended oxamido-bridged structure consisting of two pyramidal copper(II) and one octahedral nickel(II) ions. The central Ni(II) and two terminal Cu(II) ions are antiferromagnetically coupled, J?=???60.2?cm?1. 相似文献
19.
Y. Kim H. G. Koo D. H. Shin L. O. Park J. H. Lee H. G. Jang C. Kim 《Journal of Structural Chemistry》2010,51(2):382-385
In the crystal of K4[Zn(Citrate)2], two citrate anions coordinate Zn(II) cation with octahedral geometry in the [Zn(Citrate)2]4− complex anion, and the charge is balanced by four potassium ions. Crystal data: monoclinic, P21/c, a = 8.502(2) ?, b = 13.210(3) ?, c = 8.942(2) ?, β = 113.132(4)°, V = 923.5(4) ?3, Z = 2, R = 0.0229. 相似文献
20.
I. A. Koval' K. B. Yatsimirskii S. Trofimenko V. V. Pavlishchuk 《Theoretical and Experimental Chemistry》1998,34(6):323-326
The new trinuclear complex K{(CoTpt-Bu)[Fe(CN)6](CoTpt-Bu)}, in which the initial structural fragments are linked by CN− bridges, was synthesized by the directed stitching of mononuclear complexes, one of which was [Fe(CN)6]3− while the other was cobalt(II) tris(3-tert-butyl-l-pyrazolyl)borate ([(CoTpt-Bu)]+). The magnetic moment of K{(CoTpt-Bu)[Fe(CN)6](CoTpt-Bu)} at 292 K was 8.07 μβ (S=7/2), indicating the absence of antiferromagnetic exchange interactions in the trinuclear complex.
Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 34, No. 6, pp. 351–354, November–December, 1998. 相似文献