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1.
Sun Xian-Ru Cheng Peng Cui Jian-Zhong Liao Dai-Zheng Jiang Zong-Hui Yan Shi-Ping Wang Geng-Lin 《Transition Metal Chemistry》1997,22(1):65-67
Three new cobalt(II) binuclear complexes have been prepared and characterized, namely [Co2(TCPHTA)(L)4](ClO4)2 [L=1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline(NO2-phen) and 2, 2-bipyridyl (bipy), respectively], where TCPHTA is the tetrachlorophthalate dianion. Based on i.r. spectra, elemental analyses and conductivity measurements, tetrachlorophthalato-bridged structures consisting of two cobalt(II) ions in which each cobalt(II) ion has a distorted octahedral environment are proposed for these complexes. The temperature dependence of the magnetic susceptibility for [Co2(TCPHTA)(L)4](ClO4)2·nH2O (L=phen, NO2-phen and bipy) has been measured over the 77–300 K range and the observed data successfully simulated by an equation based on the spin Hamiltonian operator (H=–2JS1S2), giving the exchange integral J=–2.92, –3.45, –4.03 cm–1, respectively. This result indicates the presence of a weak antiferromagnetic spin exchange interaction between the metal ions. 相似文献
2.
Ming-Ming Miao Dia-Zheng Liao Zong-Hui Jiang Geng-Lin Wang 《Transition Metal Chemistry》1995,20(4):399-401
Summary Four novel MnII binuclear complexes have been prepared and characterized, namely: [Mn2(TBPHTA)(L)4](ClO4)2 [L = 2,2-bipyridyl (bipy), 1,10-phenanthroline (phen), 4,4-dimethyl-2,2-bipyridyl (Me2bipy) and 5-nitro-1,10-phenanthroline (NO2-phen), respectively], and TBPHTA = the tetrabromophthalate dianion. Based on i.r. spectra, elemental analyses and conductivity measurements, extended tetrabromophthalato-bridged structures consisting of two MnII ions, in which each MnII ion has a distorted octahedral environment, are proposed for these complexes. The temperature dependence of the magnetic susceptibility for [Mn2(TBPHTA)(phen)4] (ClO4)2·H2O was measured over the 4–300 K range and the observed data were successfully simulated by an equation based on the spin Hamiltonian operator ( = -2J
1
2), giving the exchange integral J = -1.22 cm–1. This result indicates a weak antiferromagnetic spin exchange interaction between the metal ions. 相似文献
3.
Five chloroanilato-bridged manganese(II) binuclear complexes, [Mn2(CA)L4](ClO4)2, where L = 4,4′-dimethyl-2,2′-bipyridine (Me2-bpy), 5-methyl-1,10-phenanthroline (Me-phen), 5-chloro-1,10-phenanthroline (Cl-phen), 5-nitro-1,10-phenanthroline (NO2-phen) and 2,9-dimethyl-1,10-phenanthroline (Me2-phen), and CA represents the dianion of chloroanilic acid, have been synthesized and characterized by elemental analyses,
molar conductivity and room temperature magnetic moment measurements, and by spectroscopy. It is proposed that these complexes
have CA-bridged structures and consist of two manganese(II) ions in a distorted-octahedral environment. The complexes [Mn2(CA)(Me2-bpy)4](ClO4)2
(1) and [Mn2(CA)(Me-phen)4](ClO4)2
(2) were characterized by variable temperature magnetic susceptibility measurements (4–300 K) and the observed data were successfully
simulated by an equation based on the spin Hamiltonian operator, Ĥ = −2JŜ
1
Ŝ
2, giving the exchange integral J = −1.98 cm−1 for (1) and J = −2.41 cm−1 for (2). This result indicates that there is a weak antiferromagnetic spin-exchange interaction between the two MnII ions within each molecule.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
4.
Three new binudear cobalt (II) complexes with extended te-tracarboxylato- bridge have been synthesized and characterized, namely [Co2 (PMTA) (bpy)4] (1), [Co2(PMTA)-(phen)4] (2) and [Co2(PMTA) (NO2phen)4] (3), where PMTA represents the tetraanion of pyroniellitic acid, and bpy, phen, NO2-phen denote 2,2'-bipyridine, 1,10-phenan-throline; 5-nirto-1, 10-plienanthroline, respectively. Based on elemental analyses, molar conductivity measurements, IR and electronic spectra studies, it is proposed that these complexes have PMTA-bridged structures and consist of two cobalt (II) ions, each in a distorted octahedral environment. These complexes were further characterized by variable temperature magnetic susceptibility measurements (4-300 K) and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, giving the exchange integral J = - 1.02 cm-1 for 1, J = -1.21 cm-1 for 2 and J = - 1.18 cm-1 for 3, respectively. These results revealed the operation of antiferromagneti 相似文献
5.
Summary Manganese(II) complexes of bis(2-benzimidazolylmethyl) ether (DGB), bis(2-benzimidazolylmethyl) sulphide (TGB) and the n-butyl derivative of DGB (BDGB) were prepared and characterised. The solution e.p.r. spectrum of [Mn(TGB)Cl2] in DMF at 143 K is commensurate with an axially distorted monomeric manganese(II) complex, room temperature magnetic moment
(6.04 B.M.) per manganese(II) atom being in the range found for other d5 monomeric manganese(II) complexes. The solution e.p.r. spectrum of [Mn(BDGB)Cl2]-2H2O in DMF at 143 K indicates the presence of two equivalent manganese(II) ions coupled by an exchange interaction, fostered
by bridging chlorides. Evidence for this is provided by a nearly isotropic 11 line hyperfine structure of 55Mn, with a coupling constant 45 ± 5G. Contact-shifted 1H n.m.r. data also supports an exchange coupled dimeric manganese complex. The room temperature magnetic moment, 5.64 B.M.,
per manganese(II) indicates quenching of the magnetic moment below that of monomeric manganese(II) ion. The [Mn(DGB)Cl2]·H2O complex exhibits a magnetic moment of 6.02 B.M. per manganese, indicating a monomeric manganese complex. E.p.r. data of
the complex diluted in an analogous Zn-DGB complex (1∶20) correlates well for D = 0.22cm−1 and λ ∼- 0.267. The [Mn(DGB)-(C1O4)2] and [Mn(BDGB)(ClO4)2] complexes, diluted in analogous Zn-DGB and Zn-BDGB complexes (1∶20), show a strong single e.p.r. line at g
eff ∼- 2. The complexes have low magnetic moments; 4.44 B.M./Mn and 4.39 B.M./Mn, at room temperature. 相似文献
6.
Shi Jingmin Xu Jiqing Wang Renzhang Yang Guoyu Sun Haoran Wang Tiegang Cheng Peng Liao Daizheng 《Transition Metal Chemistry》1998,23(5):629-630
Three novel binuclear CoIIcomplexes, [Co2(TAE)-(phen)4](ClO4)2·3H2O(1),[Co2(TAE)(Nphen)4](ClO4)2 ·4H2O(2) and [CO2(TAE)(bipy)4](ClO4)2·H2O(3) (TAE=tetraacetylethene dianion, phen=1,10–phenanthroline, Nphen=5–nitro·1,10–phenanthroline, bipy =2,2-bipyridy1), have been synthesized and characterized by elemental analysis, i.r., molar conductance and electronic reflection spectra. The complexes are proposed to contain tetraacetylethene dianion bridged structures and two CoII ions. The variable-temperature magnetic susceptibility of complex (1) was measured in the 4–300 K range. The magnetic coupling parameter is consistent with antiferromagnetic exchange between the two CoII centres and the data fit a binuclear magnetic exchange model based on the Hamiltonian operator ( = –2 J12, S1=S2=3/2), giving the antiferromagnetic coupling parameter of 2J=–1.55cm–1. 相似文献
7.
本文合成了两个新型双核配合物, [Cu(Samen)Co(L)2]和[Cu(Sampn)Co(L)2], Samen^4^-表示N,N'-双水杨酰代乙二胺根阴离子,Sampn^4^-表示N,N'-1,2-双水杨酰代丙二胺根阴离子, L表示5-硝基-1,10-菲咯啉(NO2-Phen)。经元素分析, IR和电子光谱等推定配合物具有酚氧桥结构,Cu(II)及Co(II)的配位环境分别为平面四方及畸变八面体构型。测定了配合物(4-300K)的变温磁化率, 并用最小二乘法和自旋Hamiltonian算符,H=2JS1.S2-DSzl导出的磁方程拟合, 求得交换参数为J=-4.39(Samen)和-3.59cm^-^1(Sampn), 表明两个Cu(II)-Co(II)双核配合物中有弱的反铁磁性超交换相互作用。 相似文献
8.
Verónica Arancibia M. Angélica del Valle Mario Bodini 《Transition Metal Chemistry》1995,20(2):179-184
Summary MnII forms a yellow mononuclear species with the title ligand having a 12 stoichiometry and whose conditional stability constant is 8.9 × 1010
m
–2. The c.v. of this complex shows an oxidation at +0.78V versus s.c.e. Controlled-potential electrolysis at +0.80V versus s.c.e. yields a binuclear species of MnIII with a 12 metal:ligand stoichiometry.The addition of MnIII(urea)6(ClO4)3 to a solution of the ligand produces a mononuclear complex of MnIII if the concentration of the metal ion is less than 1 mM. At higher concentrations a binuclear species is obtained. The latter is reduced in two steps, at +0.24 and –0.58 V versus s.c.e. Controlled-potential electrolysis at 0.0 V produces a dark green complex after the transfer of 0.5 equivalents of charge per mole of Mn. This binuclear L2MnII-MnIIIL2 mixed-valence complex can be obtained only by electrolysis of the binuclear L2MnIIIMnIIIL2 species. Attempts to prepare the complex chemically were unsuccessful - the binuclear MnIII species was obtained in every case.Author to whom all correspondence should be directed. 相似文献
9.
Shi Jing-Min Liao Dai-Zheng Cheng Peng Jiang Zong-Hui Wang Geng-Lin 《Transition Metal Chemistry》1997,22(3):209-210
The heterobinuclear complex, [CuMn(L)(phen)2](ClO4)2· H2O, [L = N,N-bis(N-hydroxyethyleneamine)oxamido, phen=1,10-phenanthroline], has been synthesized with N,N-bis(N-hydroxyethylaminoethyl)oxamido as the bridging ligand. The electronic reflectance spectrum indicates the presence of exchange-coupling interaction between bridging MnII and CuII ions. The variable-temperature magnetic susceptibility of the complex was measured over the 4–300K range. The magnetic coupling parameter is consistent with an antiferromagnetic exchange between the MnII ion and CuII ion and fits the data for a heterobinuclear CuII–MnII magnetic exchange model based on the Hamiltonian operator (H= –2JS1S2, S1=1/2, S2=5/2), giving the antiferromagnetic coupling parameter of 2J=–74.0cm–1. 相似文献
10.
Summary Binuclear NiII and CoII complexes derived from 2,6-diformyl-4-methylphenol and various aromatic monoamines have been prepared and investigated. The NiII complexes have Ni2LCl3 composition while the CoII complexes have Co2L2Cl2 composition, where L represents the organic ligand. The complexes are active catalysts in the oxidation of 3,5-di-t-butylcatechol (3,5-DTBC) by dioxygen, but less so than their Cu analogues. This result is attributed to the absence of antiferromagnetic coupling between the metal centres. 相似文献
11.
YANG Rui-Na XUE Bao-Yu WANG Dong-Mei JIN Dou-Man Henan Institute of Chemistry Zhengzhou Henan ChinaCHEN Jun LI Ming-Xing Department of Chemistry Fudan University Shanghai China 《中国化学》1997,15(1):76-83
At room temperature, dibenzoyl peroxide undergoes oxidative addition reaction with metallic copper powder and pyridine N-oxide (triphenylphosphine oxide or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolin) which affords the last products as binuclear copper(II) complexes, [Cu(C5H5NO)-(C6H5COO)2]2(1), [Cu(OPPh3)(C6H5COO)2]2(2) and [Cu(C6H5COO)(C26H2oN2)](3, C26H2oN2 is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolin). The structure of the complexes were characterized by elemental analyses, IR spectra, TG-DTA and magnetic property. Crystals(1) are triclinic, space group P1,a=0.92617(36),b=1.06973(17), c=1.08813(29) nm, a=59.60(2)°, β=74.83(3)°,γ=72.80(2)°, V=0.880 nm3, Dc=1.520 g/cm3, Z=1, R=0.044, Rw=0.048, Mr=805.78, 3477 reflections with I > 3σ(I). Each copper(Ⅱ) ion is coordinated by two bridging bidentate benzoate ligands and one pyridine N-oxide or triphenylphosphine oxide to form dimeric binuclear molecules. The structure of the compound(1) shows a clear centre of symmetry. 相似文献
12.
Xian-Ru Sun Ming-Ming Miao Peng Cheng Dai-Zheng Liao Zong-Hui Jiang Gen-Lin Wang 《Transition Metal Chemistry》1996,21(3):270-272
Summary Two novel MnII-MnIII-MnII oxalato complexes have been synthesized and characterized, namely [Mn2Mn(ox)3(L)4](ClO4) [L = 1,10-phenanthroline (phen) or 5-nitro-1,10-phenanthroline (NO2-phen), respectively], where ox stands for the oxalate dianion. Based on i.r., elemental analyses and electronic spectra, these complexes are proposed to have extended oxalatobridged structures consisting of MnII and MnIII ions, in which MnIII and each MnII ion has a distorted octahedral environment. The temperature dependence of magnetic susceptibility for [Mn2Mn(ox)3(phen)4] (ClO4) was measured over the 4.1–300 K range and the observed data were successfully simulated by an equation based on the spin-Hamiltonian operator ( = -2J(
1
2 +
2
3)), giving the exchange integral J = -1.57cm–1. This indicates weak antiferromagnetic spin exchange interaction between MnII and MnIII ions. 相似文献
13.
合成了分子式为[Ln~2(phen)~2L],phen=C~1~2H~8N~2[ALn=Nd,L=(CH~3COO)~4(ONO~2)~2,BLn=Sm,L=(C~6H~5COO)~6,CLn=Eu,L=(C~6H~5COO)~6]3种同双核配合物。用X射线四圆衍射仪测定了3种化合物的结构。在化合物A分子中,2个Nd(III)原子由4个CH~3COO^-基团桥联,以phen和ONO~2^-为端基,构成了一个具有C~2对称性的双核分子。配合物B和C具有完全相同的结构,它们是以4个苯甲酸根为桥,2个phen和2个C~6H~5COO^-为端基的中心对称双核分子,其中6个苯甲酸根的成键状态可分为3种状况。在3种化合物中,每个Ln均为9配位,呈不规则多面体。Ln-Ln距离,A为0.397nm,B和C均为0.405nm。测定了各配合物的变温磁化率,通过对磁性质研究,发现化合物A在低温下具有反铁磁物质行为,并由理论拟合,求得了磁参数g,J值。 相似文献
14.
系列双核Ln(III)配合物的晶体结构和磁性 总被引:1,自引:0,他引:1
合成了分子式为[Ln~2(phen)~2L],phen=C~1~2H~8N~2[ALn=Nd,L=(CH~3COO)~4(ONO~2)~2,BLn=Sm,L=(C~6H~5COO)~6,CLn=Eu,L=(C~6H~5COO)~6]3种同双核配合物。用X射线四圆衍射仪测定了3种化合物的结构。在化合物A分子中,2个Nd(III)原子由4个CH~3COO^-基团桥联,以phen和ONO~2^-为端基,构成了一个具有C~2对称性的双核分子。配合物B和C具有完全相同的结构,它们是以4个苯甲酸根为桥,2个phen和2个C~6H~5COO^-为端基的中心对称双核分子,其中6个苯甲酸根的成键状态可分为3种状况。在3种化合物中,每个Ln均为9配位,呈不规则多面体。Ln-Ln距离,A为0.397nm,B和C均为0.405nm。测定了各配合物的变温磁化率,通过对磁性质研究,发现化合物A在低温下具有反铁磁物质行为,并由理论拟合,求得了磁参数g,J值。 相似文献
15.
《Journal of Coordination Chemistry》2012,65(11):1725-1730
A binuclear copper(II) complex [Cu2 (μ-pyo)2Br4] n (where pyo = pyridine N-oxide) has been synthesized and its structure determined by X-ray crystallography. This complex crystallizes in monoclinic, space group P21/c, with unit cell dimensions a = 11.020(3) Å, b = 10.049(3) Å, c = 7.905(2) Å, β = 110.609(3)°, and Z = 2. The structure was refined to final R = 0.0311 and wR = 0.0721 for 1302 observed reflections (I > 2σ(I)). In the complex, two Cu(II) ions are bridged by two pyo ligands and four bromides coordinate the Cu(II); the distance between the bridged Cu(II) ions is 3.261 Å. The variable-temperature (4–300 K) magnetic susceptibility data show that the magnetic moment is zero. Thus, there exists very strong anti-ferromagnetic coupling between the bridged binuclear Cu(II) ions. Density functional calculations yield a singlet-triplet splitting 2J = ?1355 cm?1. 相似文献
16.
Zong-Hui Jiang Chao-Li Deng Dai-Zheng Liao Shi-Ping Yan Geng-Lin Wang 《Transition Metal Chemistry》1993,18(3):345-347
Summary Four new trinuclear copper(II) complexes, [Cu(phen)-(NBzIm)] (ClO4) (1), [Cu(bpy)(NBzIm)](ClO4) (2), [Cu-(Me2-bpy)(NBzIm)](Ac)·1/2H2O (3) and [Cu(Me2-bpy)-(Im)](ClO4)·1/2H2O (4) (phen = 1, 10-phenanthroline, bpy = 2,2-bipyridine, NBzIm = 6-nitrobenzimidazolate ion, Im=imidazolate ion) have been prepared and characterized by variable temperature magnetic susceptibility measurements. A weak antiferromagnetic spin exchange interaction operates between copper(II) ions, exchange integrals evaluated as J =-23.82 cm-1 for (1); and J=-21.91 cm-1 for (2). 相似文献
17.
A. Ya. Usyatinskii G. Z. Suleimanov E. A. Zul'fugarly Sh. M. Machmudov V. I. Bregadze I. P. Beletskaya 《Russian Chemical Bulletin》1993,42(3):552-554
The interaction of (CO)3MnC5H3RLi (R=2-Me2NCH2, H) with 2-Ph-1-HgBr-1, 2-C2B10H10 and (1, 7-C2H2B10H9-9)TlCl2 gives the corresponding C-carboranylmercury and B-carboranylthallium derivatives with M-C bonds, in which the C atom belongs to the cyclopentadienyl ring of the substituted cymantrenyl fragment. The structures of the compounds obtained are discussed on the basis of1H NMR and IR spectral data.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 586–587, March, 1993. 相似文献
18.
Novel binuclear substituted manganese(I) carbonyls [Mn(CO)4?nLn]2(μ-N-N)2 (n = 1, (N-N)2 = biimidazolate, L = PBun3; (N-N)2 = bibenzimidazolate, L = P(OMe)3, P(OPh)3, PPh3, PEt3 or PBun3, as well as n = 2; (N-N)2 = biimidazolate, or bibenzimidazolate, L = PBun3, PEt3 or P(OMe)3) are described, in which the anions (N-N)2 act as tetradentate bridging-groups. They were prepared by treating [Mn(CO)4(μ-Br)]2 with thallium or potassium salts of 2,2′-biimidazole or 2,2′-bibenzimidazole and subsequent displacement of CO by L. The structures of the complexes are discussed. 相似文献
19.
Tameryn Stringer Prinessa Chellan Bruno Therrien Nelusha Shunmoogam-Gounden Denver T. Hendricks Gregory S. Smith 《Polyhedron》2009,28(14):2839-2846
A series of binuclear palladium(II) salicylaldiminato dithiosemicarbazone complexes have been synthesized and characterized. The palladium complexes were obtained by the reaction of various ethylene- and phenylene-bridged dithiosemicarbazones with Pd(PPh3)2Cl2. The free salicylaldimine ligands and their palladium complexes were characterized by NMR and IR spectroscopies, ESI-mass spectrometry, elemental analyses and for two representative complexes also by X-ray diffraction. In both metal complexes, the solid-state structures show the two palladium centers to be coordinated in a slightly distorted square-planar geometry, which gives rise in each case to five- and six-membered chelate rings. The salicylaldimine thiosemicarbazone ligands coordinate to palladium in a tridentate manner, through the phenolic oxygen, imine nitrogen and thiolate sulfur atoms. 相似文献
20.
本文合成了两个新的双核配合物, [Cu(sampu)Ni(L)2], sampn^4^-表示N,N'-1,2-丙二水杨酰胺阴离子, L表示2,2-联吡啶(bpy)或1,10-菲咯啉(phen),经元素分析, IR和电子光谱等方法已推定配合物具有酚氧桥结构和Cu(II)及Ni(II)的配位环境分别为平面四方及八面体构型, 配合物的变温磁化率已测(4-300K), 其数值用最小二乘法和从自旋哈密顿算符H=-2JS1S2导出的磁方程拟合, 求得交换参数为J=-1.90cm^-^1(pby)和J=1.68cm^-^1(phen), 表明两个Cu(II)-Ni(II)双核配合物中有弱的反铁磁自旋交换相互作用。 相似文献