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1.
镍(Ⅱ)和铜(Ⅱ)的双核大鸟配合物的电化学研究 总被引:2,自引:0,他引:2
用叔丁基-2,6-二甲酰基苯酚与4-正己基硫脲缩合成大鸟配体,用循环伏安法研究了它与Ni~(2+)及Cu~(2+)生成的双核配合物的氧化还原过程,探讨了两中心原子间的作用,测定了电极反应速率常数。此外,还研究了配合物与CO的键合,并用红外光谱证实了Ni(Ⅱ)配合物有活化CO的能力。 相似文献
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吡啶-2,6-二甲酸经酯化,肼解得吡啶-2,6-二甲酰肼(2),(2)与芳香醛缩合得到了3个新的酰腙配体:吡啶-2,6-二甲酰肼苯甲醛腙(3a)、吡啶-2,6-二甲酰肼水杨醛腙(3b)和吡啶-2,6-二甲酰肼呋喃甲醛腙(3c),其结构经元素分析、IR、1HNMR和MS进行了确认。制备了吡啶-2,6-二甲酰肼与这三种新型配体的Tb(III)和Eu(III)配合物,并对配合物的溶液态的荧光性质进行了研究。结果表明,吡啶-2,6-二甲酰肼苯甲醛腙(3a)和吡啶-2,6-二甲酰水杨醛腙(3b)作为荧光敏化剂,对Eu3+和Tb3+的荧光敏化性能比吡啶-2,6-二甲酰肼以及大多数吡啶-2,6-二甲酸衍生物要好,是较理想的稀土荧光敏化剂,它们的稀土配合物在分子偶极矩较小的溶剂中荧光强度较强。 相似文献
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《化学研究与应用》2016,(9)
氯化-二[N-(2,6-二异丙基苯基)-N'-苯基-戊烷-2,4-二亚胺基]镱L_(ph2)~(2,6-iPr)YbCl(L_(ph)~(2,6-iPr)=[2,6-~iPr_2-C_6H_3-NC(Me)CHC(Me)N-C_6H_5])与2,6-二叔丁基-4-甲基苯酚钠按1:1摩尔比发生配体取代反应,得到了二芳氧基镱配合物L_(Ph)~(2,6-iPr)Yb(OC_6H_2-4-Me-2,6-~tBu_2)_2(1);N,N'-二-(2,6-二甲基苯基)-戊烷-2,4-二亚胺基钠(L~(2,6-Me)Na=Na[(2,6-(Me)_2-C_6H_4NC(Me)CHC(Me)N-C_6H_4-2,6-(Me)_2])与YbCl_3按3:1的摩尔比反应的脱质子产物,与对叔丁基苯酚按1:0.94的摩尔比进行反应,也发生了配体取代反应,得到了二芳氧基镱配合物YbL~(2,6-Me)(OC_6H_4-4-tBu)_2·2THF(2)。产物1和2分别在甲苯和己烷中结晶,其结构经过元素分析和X-射线单晶衍射表征,发现配合物1和2的晶体结构受到配体的空间位阻的影响而发生变化。 相似文献
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2,6-二羟甲基吡啶(1)经活性MnO_2氧化得到2,6-二甲酰基吡啶(2)。邻硝基苯酚与N-取代的二(氯乙基)胺在DMF溶液中反应,得到N-取代的1,5-二(邻硝基苯氧基)-3-氮杂戊烷(3a~3c),再经水合肼/Raney Ni还原,获得N-取代的1,5-二(邻氨基苯氧基)-3-氮杂戊烷(4a~4c)。利用Ba~(2 )作为模板离子,(2)分别与(4a~4c)反应,合成了一类新的含吡啶环系西佛碱大环配合物Ⅰ~Ⅲ,配合物Ⅰ、Ⅲ经与NaBH_4的乙醇溶液还原解络,得到氮杂大环自由配体Ⅳ和Ⅴ。所有西佛碱大环配合物和氮杂大环自由配体均经元素分析、IR、~1H NMR、MS等证实了它们的结构和组成。 相似文献
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利用2,6-二甲基吡啶作为起始物合成了不对称前驱体6-乙酰基-2-乙酯基吡啶,在此基础上合成了单亚胺吡啶配体(5)和相应的Co(II)配合物二氯·{2-乙氧甲酰基-6-[1-[(2,6-二乙基苯)亚胺基]乙基]吡啶}合钴(II)(6)。晶体结构分析表明:配体5作为三齿配体以[N, N, O]原子和两个氯离子与中心钴(II)配位,形成畸变的三角双锥配位环境,其中吡啶氮原子和两个氯原子形成赤道平面。将该钴配合物作为催化剂应用于乙烯的聚合过程,以MAO为助催化剂,在15.5ºC下作用1 h,可达到1.820×104 g/mol-Co∙h∙atm的催化活性。 相似文献
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廿员大环双核铜(II)配合物的合成和对超氧歧化酶的摸拟 总被引:5,自引:0,他引:5
本文合成了六个新的廿员大环双核铜(II)配合物作为Cu,Zn-SOD模拟物, 其配体是用2,6-二甲酰基吡啶与1,3一丙二胺缩合而成, 以SCN,Cl-Br-,I-,N3-,OH-桥联, 用多种物理方法进行表征, 并用核黄素光照法研究与O2-反应的动力学, 结果表明, 反应速率常数大约在107mol-1.Clm3,S-1其中以SCN为桥的配合物速率常数最高,而含N3-桥的最低, ESR谱研究结果表明前者与O2-为可逆的催化反应, 后者为不可逆的氧化还原反应, 这种情况与作者曾研究过的二乙酰基吡啶缩丙二胺合铜配合物一致, N3-桥对配合物的阻化作用与N3-对SOD的阻化作用类似。 相似文献
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N,N''-双(3-甲酰基-4-羟基苯甲酸甲酯)缩环己二胺Schiff碱过渡金属配合物的合成及表征 总被引:2,自引:0,他引:2
在N2气保护下,3-甲酰基-4-羟基苯甲酸甲酯与环己二胺在无水乙醇中缩合反应合成了新型的Schiff碱配体N,N'-双(3-甲酰基-4-羟基苯甲酸甲酯)缩环己二胺,收率为66.7%.该配体与四水合醋酸锰在无水乙醇中反应,并经空气氧化、氯化锂处理得到Mn3+配合物;与三氯化铁、氯化镍在无水乙醇中配位分别得到Fe3+、Ni2+配合物.并通过红外光谱、核磁共振、元素分析等测试方法对配体和配合物结构进行了表征. 相似文献
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本文合成了六个新的廿员大环双核铜(II)配合物作为Cu,Zn-SOD模拟物, 其配体是用2,6-二甲酰基吡啶与1,3一丙二胺缩合而成, 以SCN,Cl-Br-,I-,N3-,OH-桥联, 用多种物理方法进行表征, 并用核黄素光照法研究与O2-反应的动力学, 结果表明, 反应速率常数大约在107mol-1.Clm3,S-1其中以SCN为桥的配合物速率常数最高,而含N3-桥的最低, ESR谱研究结果表明前者与O2-为可逆的催化反应, 后者为不可逆的氧化还原反应, 这种情况与作者曾研究过的二乙酰基吡啶缩丙二胺合铜配合物一致, N3-桥对配合物的阻化作用与N3-对SOD的阻化作用类似。 相似文献
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[Co(C~5H~5)~2]~n.[M(dmit)~2](M=Ni,Pd;n=0,1,2)型配合物的合成及表征 总被引:4,自引:0,他引:4
二茂金属[M'(C~5H~5)~2]^1^+的盐与(NBu~4)~n[M(dmit)~2](M=Ni, Pd; N=1,2)反应, 当M'=Fe, Ni; n=1时, 分别得到了导电配合物[Ni(dmit)~2]和[Pd(dmit)~2]; 当M'=Co, n=1,2时, 分别得到的是电荷几乎不转移的4个盐[Co(C~5H~5)~2]~n[Ni(dmit)~2]和[Co(C~5H~5)~2]~n[Pd(dmit)~2]。用ESCA、Raman谱及循环伏安图讨论了上述化合物形成时的电荷转移量。尽管[M(dmit)~2]的室温电导率相当大, 但其电导率随温度的变化曲线表明它们属于半导体。EHCO能带计算给出[Ni(dmit)~2]的能隙0.112eV, 与实测的电导活化能相当接近。 相似文献
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首次报道了新型Schiff碱配合物-双[N,N'-亚乙基-2,2'-(苯亚甲基)二(3,4-二甲基吡咯-5-醛缩亚胺)]合单金属配合物MH~2[M-Mn(Ⅱ)、Fe(Ⅲ)Cl、Cr(Ⅲ)Cl、Cu(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)的合成方法及光谱特征。 相似文献
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含二茂铁基为臂的三角架型过渡金属配合物的研究 总被引:2,自引:0,他引:2
本文利用2,2',2'-三氨基三乙胺(tren)与二茂铁甲醛(FcCHO)的Schiff碱缩合产物(L)为配体合成了十个三角型过渡金属配合物:[MLX]^2+/1+,M=Zn^2+,Cu^2+,Ni^2+,Co^2+=和MN^2+,X=H~2O或OAc^-,并用电子光谱、红外光谱和顺磁=共振光谱对配合物的结构进行了表征.测定了四个化合物的变温磁化率,实验结果表明二茂铁中磁性的Fe(Ⅱ)离子对配合物的磁性影响很小,整个化合物只显示中心离子的磁性. 相似文献
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一维4, 4'-联吡啶桥联噻吩甲酰三氟丙酮过渡金属配合物的合成、结构和磁性 总被引:4,自引:0,他引:4
本文合成了六个4, 4'-联吡啶桥联配合物: [M(TTA)~2(μ-4, 4'-bipy)]~n,[M=Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II); TTA=噻吩甲酰三氟丙酮], 经元素分析、IR、 1^H NMR和晶体结构分析, 确定配合物具有一维无限链状结构。Mn(II)配合物的晶体属三斜晶系, 空间群PI, 晶胞参数: a=0.9549(2),b=0.9600(3), c=1.1556(3)nm, α=65.99(3), β=83.96(4), γ=68.89(3)°;V=0.9017(4)nm^3; Z=1; Dc=1.417g.cm^-3; μ=5.3cm^-1; F(000)=393; 最终R=0.067。Mn(II)处于畸变八面体配位环境中。由Cu(II)配合物的ESR谱近似了分子轨道系数和键合参数。Mn(II), Cu(II)配合物的变温磁化率表明, 金属离子间磁行为服从Curie定律。 相似文献
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Ovcharenko VI Fokin SV Fursova EY Kuznetsova OV Tretyakov EV Romanenko GV Bogomyakov AS 《Inorganic chemistry》2011,50(10):4307-4312
The crystals of heterospin complexes [M(hfac)(2)L(2)] (where M = Cu, Ni, Co, or Mn; hfac = hexafluoroacetylacetonate; and L = nitronyl nitroxide, 4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl) were found to make unusual jumping motions. Under ambient conditions, the jumping and various displacements of crystals lasted for several weeks. The mechanical motion was accompanied by the cracking and disintegration of crystals, and a solid [M(hfac)(2)(L(1))(2)] complex with the corresponding imino nitroxide 4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1H-imidazole-1-oxyl (L(1)) was detected. The jumping was accompanied by the spontaneous elimination of oxygen, the source of which was the nitronyl nitroxyl fragment of coordinated L. An X-ray study of [M(hfac)(2)L(2)] (where M = Cu, Ni, Co, or Mn) showed that the molecular structure of all [M(hfac)(2)L(2)] and their packing in the solid state were identical. The packing of [M(hfac)(2)L(2)] was concluded to be critical to the mechanical effect. In complexes with different stoichiometries or different sets of diamagnetic ligands ([Cu(hfac)(2)L](2), [Cu(hfac)(acac)L]·EtOH, [CuPiv(2)L(2)]·2CH(2)Cl(2), and [Cu(hfac)(2)L(2)Cu(2)Piv(4)]·3C(7)H(8) (where acac is acetylacetonate and Piv is trimethylacetate), or free L), the effect vanished when the packing changed. 相似文献
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某些芳香族羟肟一过渡金属配合物的红外光谱 总被引:1,自引:0,他引:1
The preparation and infrared spectroscopic studies of coordination compounds of salicylaldoxime, 2-hydroxy-acetophenone oxime, 2-hydroxy-benzophenone oxime and 2-hydroxy-4-methoxy-benzophenone oxime with copper (II), nickel (II), cobalt (II) and iron (II) have been described. The frquency of the C=N stretching vibration is usually higher in the complex than that in the ligand. The higher the frequency of the C=N vibration is, the larger the stability constant of the complex will be, but there is no quantitative relationship. In the case of complexes of salicylaldoxime with Cu, Ni, Co and Fe, &CC=N values are correlated linearly with the ionization potentials of the central metal ions. The frequency of the OH stretching vibration is closely related to the geometric configuration of the complex. Thus aromatic hydroxyoximes form coordination compound with Co (II) and Fe (II) with cis configuration possessing six membered stronger hydrogen bonding ring. This is indicated in the infrared spectra by the complete absence of the absorption band due to the OH stretching vibration, or by the appearance of an extremely broad and flat band of very low intensity. However, Cu (II) or Ni (II) complex possesses trans configuration with five membered hydrogen-bonding bridge showing characteristic OH absorption band in the infrared region. The &COH of complex investigated is closely related to the polar nature of the substituents on the benzene ring. By examining the spectra of Cu-63 and Cu-65 complexes with 2-hydroxy-4(5)-substituted benzophenone oximes, the characteristic frequencies of M -- O and M -- N in the far infrared region were assigned for a series of aromatic hydroxyoxime-transition metal complexes. 相似文献
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Single crystal polarized Raman and infrared spectra of the series Na(5)[MO(2)][X] with M = Co(I), Ni(I), and Cu(I) and X = S(2-) and CO(3)(2-), are reported. All phonon modes are assigned to the lattice eigenmodes based on the group theory analysis and first principles lattice dynamics calculations. The energies of the fundamental symmetric and asymmetric vibrations of the [MO(2)](3-) complex are discussed on the basis of their electronic structure and variation in M-O interatomic distances. Electronic Raman scattering and luminescence are observed for the magnetic members of the series (Co(I), d(8), and Ni(I), d(9)). Ligand field theory is employed to account for the electronic effects which originate from states split by spin-orbit coupling. 相似文献
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Paola Piu Vittorio Leoni M. Antonietta Zoroddu Gavina Manca Salvatore Deiana Carlo Gessa 《Transition Metal Chemistry》1992,17(4):283-286
Complexes of formula M(L)2·nH2O [M=Co or Ni; L=indole-3-carboxylic (I3CH), indole-3-acetic (I3AH), indole-N-acetic (INAH), indole-N-methyl-2-carboxylic (INMH) and M=Co or Ni and Cu, L=indole-3-β-acrylic acids (I3βH)] were pepared and characaterized by i.r.
and electronic spectroscopy and by susceptibility measurements and e.s.r. at room and low temperature. The cobalt and nickel
complexes exhibit a distorted octahedral coordination except the Co(I3C)2 complex for which a tetrahedral coordination was suggested.
The Cu(I3β)2·H2O shows e.p.r. features that can be interpreted if the triplet state, S=1, depending on the temperature, is able to migrate
through the crystal lattice of carboxylate dimers such as the copper(II) acetate monohydrate. 相似文献