大环镍配合物[Ni(teta)(NCS)2]的合成与结构研究

大环配体由于其独特的配位性能已吸引了广泛的注意,用大环化合物模拟生物功能,是当今大环化学发展的方向之一[1]。大环四胺配体5,7,7,12,14,14-六甲基-1,4,8,11-四氮杂环十四烷(简记为teta)的钴配合物已被用来作为研究维生素B12的模型分子[2],一些teta的配合物也已被陆续报道[3     

含吡啶基十四元六氮大环配体与Ni(Ⅱ)配合物的合成及性质的研究

金属四氮大环配合物的合成及性能的研究对于探讨生理过程,人工模拟具有一定的意义,本文研究的一种四氮配位的大环配合物是含有吡啶基的十四元四氮配位的大环配合物(图1),关于此类配合物的合成工作始于1974年,最早由Goedken和Paryzek合成了Fe(Ⅱ)、Mg(Ⅱ)、Zn(Ⅱ)、Sc(Ⅲ)的这类配合物。     

NaBrO3—CH2（COOH）2—H3PO4—CuL^2＋体系的振荡化学研究

四氮杂大环配合物是生物体内一些金属酶结构单元的模拟物,可作为振荡反应催化剂来加以研究.我们报道的一些四氮杂大环铜(Ⅱ)、镍(Ⅱ)配合物所参与的催化振荡反应体系中采用的底液都是稀H_2SO_4,尚未见以H_3PO_4作底液的报道。然而研究以H_3PO_4作底液的     

140Cu/MCM-41和14T2Cu/MCM-41的制备与表征

二氧四胺大环和取代二氧四胺大环化合物兼有大环氮杂冠醚和低聚肽的性质,能和很多过渡金属离子(Cu²⁺,Ni²⁺,Mn²⁺,Co²⁺等)形成具有特殊功能的配合物.如十四元二氧四胺大环Co(Ⅱ)配合物在-70℃加入过量的咪唑或吡唑后.     

双四氮杂大环镍(Ⅱ)配合物催化的化学振荡反应

四氮杂大环配合物是生物体内一些金属酶结构单元的模拟物,四氮杂大环铜和镍的配合物可以催化化学振荡反应。近年来,此类反应被广泛地研究［１～４］。目前已报道的作为化学振荡反应催化剂的四氮杂大环配合物的配体都是单环。我们发现一种双四氮杂大环镍(Ⅱ)配合物Ｎｉ２Ｌ（ＣｌＯ４）４［Ｌ为双(１１,１３二甲基１,４,７,１０四氮杂１０,１３环十三二烯１２亚甲基)］可以作为化学振荡反应的催化剂,本文研究了Ｎｉ２Ｌ（ＣｌＯ４）４催化ＮａＢｒＯ３ＣＨ２（ＣＯＯＨ）２（ＭＡ）Ｈ３ＰＯ４体系的化学振荡反应。１实验部分实验试剂:丙二酸…     

8-羟基喹啉取代大环配合物的酸分解动力学研究

合成了新型双功能化的8-羟基喹啉取代二氧四胺大环。这类新配体含有两个配位活性中心,在适当条件下,能分别与金属离子配位。根据pH电位滴定和紫外光谱实验的结果,在L(配体):M(金属离子)=1:1的情况下,8-羟基喹啉完全配位而二氧四胺大环只有部分配位,研究了在不同温度和不同酸度下8-羟基喹啉取代二氧四胺大环铜(Ⅱ)配合物酸催化的分解动力学行为。根据实验数据,提出了合理的反应机理。实验发现此类酸分解反应与以往二氧四胺大环酸分解机理有显著的不同,但大环的配位仍对该配合物的酸分解行为有很大的影响。     

NiL(ClO4)2催化NaBrO3-MA-H3PO4体系振荡反应的研究

报道了一种反式Curtis环的镍(Ⅱ) 的配合物NiL(ClO4)2(L为2,4,4,9,11,11-六甲基-1,5,8,12-四氮杂环十四-1,5,8,12-四烯)催化NaBrO3-CH2（COOH）2（MA）-H3PO4体系的化学振荡反应。测得该体系的振荡范围,研究、分析了各物种浓度、自由基抑制剂和还原剂、Ag+、Hg2+以及温度对振荡反应的影响。结果表明Br-起重要动力学控制作用,在反应过程中有自由基、Br2产生并参与了反应。同时发现搅拌速度对反应有很大影响。该反应的振荡轨迹与经典BZ反应及其它四氮杂大环配合物催化的体系有所不同。     

合成大环化合物的模板反应

模板反应(Template Reactions)是合成大环化合物或配合物的一种新方法。大环配合物的研究工作早在本世纪初就开始了。但在六十年代以前多为天然大环化合物,人工合成的大环化合物只有零星报道。由于人工合成的大环     

四氮杂大环四烯镍(Ⅱ)配合物[Ni(TIM)]X催化BrO_3~-氧化双有机底物的振荡反应

本文报道了四氮杂大环四烯镍(Ⅱ)配合物[Ni(TIM)]X[TIM为2,3,9,10-四甲基-1,4,8,11-四氮杂环十四-1,3,8,10-四烯;X=(ClO_4)_2,ZnCl_4,(SCN)_2]催化BrO_3~-CH_2(CO_2H)_2-(CO_2H)_2-H_2SO_4体系的新型振荡化学反应.对该振荡反应体系进行了多方面的研究,并提出了简要的机理.     

包结物[H2(teta)]2+·2Cl-·3H2O的合成与结构研究

大环化合物在生命和材料科学中很重要[1,2]。大环四胺配体5,7,7,12,14,14 六甲基 1,4,8,11 四氮杂环十四烷(teta)近年来引起了广泛关注[3,4]。我们合成了化合物[H2(teta)]2+·2Cl-·3H2O,测定了晶体结构。1　实验部分1.1　[H2(teta)]2+·2Cl-·3H2O的合成[5]将5mL0 4mmolHCl水溶液缓慢加入teta·2H2O(0 0641g,0 2mmol)的5mL甲醇溶液。连续搅拌半小时后过滤,无色滤液在室温下放置两天后长出淡黄色块状晶体。元素分析(计算值)%:C,47 58(46 71);H,10 53(10 78);N,13 68(13 62).IR(cm 1):3331(vs),3231(s),3186(vs),2973(s),2876(s)…     

(H2teta)2{[Ni(teta)][Fe(CN)6]2}•17H2O (teta＝5,7,7,12,14,14-Hexa-methyl-1,4,8,11-tetraazacyclotetradecane)超分子化合物的合成、晶体结构和磁性质研究

将Ni(teta)(ClO₄)₂ (teta＝5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)的DMF溶液和K₃[Fe(CN)₆]的水溶液在填充了琼脂冻胶的U型管中通过扩散反应, 得到了标题化合物(H₂teta)₂{[Ni(teta)][Fe(CN)₆]₂}•17H₂O, 该化合物晶体属三斜晶系, 空间群P1, 晶胞参数为a＝0.9998(2) nm, b＝1.5514(3) nm, c＝1.6647(4) nm, α＝114.15(2)°, β＝100.91(2)°, γ＝93.42(2)°, V＝2.2863(10) nm³, z＝1, D_c＝1.196 g•cm^－3, F(000)＝890, μ＝5.84 cm^－1, GOF＝0.894, R₁＝0.0582, wR₂＝0.1446 [I＞2σ(I)]. 该化合物的基本单元由2个[H₂teta]^2＋阳离子、1个{[Ni(teta)][Fe(CN)₆]₂}^4－阴离子和17个水分子组成, 它们之间通过N—H…N氢键而形成具有二维平面结构的超分子化合物. 1.8～300 K变温磁化率研究表明, 化合物中三核体系Fe (s＝1/2)-Ni (s＝1)-Fe (s＝1/2)中心原子间通过氰基桥联而发生强的铁磁相互作用, 磁参数J＝4.33 cm^－1, g＝2.6, θ＝60 K. 通过TG-DTG测定了配合物的热稳定性.     

Synthesis and magnetic properties of the one-dimensional linear chain structure cyano-bridged complex [Cu(teta)(H2O)2][Cu(teta) Fe(CN)6]ClO4·2H2O (teta=5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacylotetradecane)

Reaction of either K₃[Fe(CN)₆] or K₄[Fe(CN)₆] with a macrocyclic Cu^II complex, [Cu(teta)](ClO₄)₂ (teta = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacylotetradecane), in aqueous solution gave the same product as shown by spectroscopic and physicochemical characterisation. The crystal structure of the complex shows that it is a one-dimensional linear chain type heterobinuclear Fe^III–Cu^II polymer. The unit is composed of a [Cu(teta)(H₂O)₂]²⁺ cationic complex, a Fe^III–Cu^II alternate linear chain unit, a ClO ₄ ^– ion and four water molecules. The Cu atom is coordinated in a distorted octahedral arrangement by four nitrogen atoms from one teta ligand and two nitrogen atoms of the bridging cyanide groups. The Cu—N bond distances involving the cyanide bridges, 2.522(7) and 2.608(7)Å, respectively, indicate weak antiferromagnetic interactions between the Fe^III and Cu^II atoms.     

Synthesis and Crystal Structure of an Ion-pair Compound: [H_2(teta)]~(2+)·[Ni(CN)_4]~(2-)·2H_2O (teta = Meso-5,7,7,12,14,14-hexamethyl- 1,4,8,11-tetraazacyclotetradecane)

1INTRODUCTION The macrocyclic compounds play an important ro-le in life science and materials science[1].In recent years,teta has gained extensive attention as a raw material of crystal engineering,and its coordination behavior with metallic ion has been …     

Structural Evidence of Anion's Effect on the Ion Packing of [Ni2(teta)3]4+ in the View of H-bonding Interaction

Two dinuclear nickel(II) complexes [Ni2(teta)3]Cl4·2H2O 1 and [Ni2(teta)3](NO3)4 2 (teta = triethylenetetramine) were synthesized by a solvothermal method and structurally characterized. Complex 1: orthorhombic, Pbca, a = 13.791(3), b = 13.078(3), c = 18.323(4) , V = 3304.8(12) 3, Z = 4, Mr = 733.98, Dc = 1.475 g/cm3, μ = 1.500 mm-1, F(000) = 1560, R = 0.0585 (I > 2σ(I)) and wR = 0.1243. Complex 2: orthorhombic, P212121, a = 7.8279(14), b = 14.209(3), c = 31.163(6) , V = 3466.2(11) 3, Z = 4, Mr = 804.19, Dc = 1.541 g/cm3, μ = 1.164 mm-1, F(000) = 1704, R = 0.0401 and wR = 0.0840 for 5950 observed reflections (I > 2σ(I)). Two Ni2+ ions are connected by one linear bridging teta ligand, forming a dinuclear [Ni2(teta)3]4+ cation. Each Ni2+ ion in 1 and 2 takes a distorted octahedral geometry with six coordinated N atoms from two teta ligands. The effect of different anions on the arrangement of [Ni2(teta)3]4+ cations has been discussed in view of H-bonding interactions. Thermal stability of 1 and 2 was also investigated.     

Synthesis,IR Spectrum,Thermal Analysis,and Crystal Structure of the Cyano‐bridged Heteronuclear Polymeric Complex: [Zn(teta)Ni(μ‐CN)2(CN)2]n

The heteronuclear polymeric complex, [Zn(teta)Ni(μ‐CN)₂(CN)₂]_n (teta: triethylenetetramine), was synthesized and characterized by elementel analysis, FT‐IR spectroscopy, thermal analysis and single crystal X–ray diffraction techniques. The complex crystallizes in the monoclinic system, space group P2₁/c and in which the Zn^II ion exhibits a distorted octahedral coordination by one tetradentate teta ligand and two bridging cyano groups as a trans position, whereas the Ni^II ion has square planer coordination and is coordinated by four cyano ligands. The decomposition reaction takes places in the temperature range 30–600 °C in the static air atmosphere.     

OH(3) (-) and O(2)H(5) (-) double Rydberg anions: predictions and comparisons with NH(4) (-) and N(2)H(7) (-)

A low barrier in the reaction pathway between the double Rydberg isomer of OH(3) (-) and a hydride-water complex indicates that the former species is more difficult to isolate and characterize through anion photoelectron spectroscopy than the well known double Rydberg anion (DRA), tetrahedral NH(4) (-). Electron propagator calculations of vertical electron detachment energies (VEDEs) and isosurface plots of the electron localization function disclose that the transition state's electronic structure more closely resembles that of the DRA than that of the hydride-water complex. Possible stabilization of the OH(3) (-) DRA through hydrogen bonding or ion-dipole interactions is examined through calculations on O(2)H(5) (-) species. Three O(2)H(5) (-) minima with H(-)(H(2)O)(2), hydrogen-bridged, and DRA-molecule structures resemble previously discovered N(2)H(7) (-) species and have well separated VEDEs that may be observable in anion photoelectron spectra.