双核铁(Ⅱ)配合物的合成、晶体结构及与分子氧反应性能

合成了一个双核铁(Ⅱ)配合物[Fe2L{O2P(OPh)2}](ClO4)2Et2O(1) (L表示双核配体: N-Et-HPTB, N, N, N′, N′-四双(N-乙基-2-苯并咪唑甲基) -2-羟基-1, 3-二氨基丙烷). 测定了其晶体结构, 三斜晶系, 空间群P1, a = 1.526 8(3) nm, b = 1.259 8(3) nm, c = 1.563 0(3) nm, α = 94.41(3)°,β = 115.31(3)°, β = 99.90(3)°, V = 3.267(1) nm3 , Z = 2; R = 0.084 7, Rw = 0.177 8. Fe(Ⅱ)离子被一个烷氧原子和一个磷酸酯桥联, Fe-μ-O-Fe 键角为131.20(3)°, Fe-Fe距离为0.364 9 nm. 两个Fe(Ⅱ)均具有三角双锥几何构型. 低温下(-60℃) Fe(Ⅱ)配合物与分子氧反应生成稳定的分子氧加合物1/O2, 该加合物展示可见吸收光谱最大在606 nm, 共振Raman光谱显示两个特征吸收带, 478((Fe-O)和897 cm-1((O-O). 后者是 μ-1,2-peroxo物种的典型特征. 即在低温下铁(Ⅱ)配合物与分子氧生成了过氧化物桥联的双核铁(Ⅲ)氧加合物. 模拟了生物体内某些非血红素蛋白的活性中心的结构和功能.     

二硫代草酸根桥联的双核镍(Ⅱ)配合物研究

Three binuclear Nickel(Ⅱ) complexes were synthesized, bridged with dithiooxalate, Ni₂(Bpy)₃(Dto)₂(H₂O)₃(1), Ni₂(Phen)₃(Dto)₂(H₂O)₃(2) and Ni₂(Me₂Bpy)₃(Dto)₂(H₂O)₂ (3) (Bpy=2,2′-Bipyridine, Phen=1,10-phenanthroline, Me₂Bpy=4,4′-dimethyl-2,2′-bipyridine, Dto^2-=Dithiooxalate), and characterized by elemental analyses, IR, UV-Visible spectra, conductance. The variable temperature magnetic susceptibilities for the complexes were measured in the range of temperature between 1.5 K and 298 K. Experimental data of magnetic susceptibility were successfully fit to theoretical value based on the spin Hamiltonian operator：(?), S₁=S₂=1, giving the magnetic exchange parameters of 2J=-52.8 cm^-1. This result indicates the presence of a strong antiferromagnetic spin exchange interaction between the Ni(Ⅱ) ions. The magnetic exchange parameters of the binuclear Nickel(Ⅱ) complexes bridged with dithiooxalate is larger than that of the binuclear Nickel(Ⅱ) complexes bridged with oxalate. Dithiooxalate is more effective to transfer antiferromagnetic spin exchange interaction between the Ni(Ⅱ) ions than oxalate.     

Synthesis and Crystal Structure of a Novel Complex [Cu(Phen)3](ClO4)2(btio)(H2O)

1 INTRODUCTION There has been increasing interest of Cu(II) and phenanthroline complexes in the field of coor- dination chemistry[1～4]. At the same time, nitronyl nitroxide radicals have played a prominent role in the design and construction of molecula…     

Exchange Interaction of a Novel Heterospin Polynuclear Complex Containing Transition Metals and Imino Nitroxide Radicals: {[(CuL)Ni(IM-2Py)_2](ClO_4)_2}_2·2H_2O

IntroductionThemajorresearchaimsinthefieldofmolecularmag netismareontheonehandthedesignofmolecularassembliesthatexhibitaspontaneousmagnetizationandontheotherhandtherationalizationofmagnetostructuralcorrelation .1Polynuclearmacrocycliccomplexesandnitroxideradicalmetalliccomplexesaretwoactivefieldsofresearchfordesign ingandsynthesizingnewmagneticmaterials.2 6Polynuclearmacrocycliccomplexescontainingmul tiatomicbridgesuchasphenolateoxygen ,oxamidoandoxi amtogroupshavebeenconsiderablyinvestigated…     

一个含铜(Ⅱ)四氮大环阳离子和锰(Ⅱ)一维链阴离子化合物{[Cu(trans[14]diene)SCN]2Mn(SCN)4(4,4''''-bipy)·4H2O}n的合成和结构

报道了一维化合物{[Cu(trans[14]diene)SCN]2Mn(SCN)4(4,4'-bipy)·4H2O}n(trans[14]diene为5,7,7,12,14,14-六甲基-1,4,8,11-四氮杂十四环-4,11-二烯,4,4'-bipy为4,4'-联吡啶)的合成、表征和结构分析.该晶体属三斜晶系,具有P1-空间群.α＝0.95920(10)nm,b＝1.06800(10)nm,c＝1.7316(2)nm,α＝84.400(10)°,β＝74.850(10)°,γ＝69.650(10)°,V＝1.6053(3)nm3,Z＝1,Dc＝1.365g/cm3,F(000)＝691,最终R[I＞2σ(I)]＝0.0474,R(全部)＝0.0625,GOF(F2)＝1.222.该化合物含[Mn(SCN)4(4,4'-bipy)n]2-链和两个[Cu(trans[14]diene)SCN]+阳离子.     

From Dinuclear to Mononuclear：Co（Ⅱ） Complexes with Pyridine-2,6-Dicarboxylic Acid（H_2PDA）

Reactions of pyridine-2,6-dicarboxylic acid(H2PDA) with cobalt(Ⅱ) acetate resul-ted in two cobalt(Ⅱ) complexes,[Co(HPDA)2].2H2O.0.5CH3OH(1) and [Co2(PDA)2(H2O)5].2H2O(2),which were characterized by single-crystal X-ray diffraction,IR and electronic absorption spectra.For both complexes,every cobalt atom lies in peudo-octahedral coordination geometry,and the whole structures present 3D frameworks linked by π-π stacking interactions and extensive hydrogen bonds.Magnetic studies showed λ =-83.38 cm-1 for(1) and g = 2.50 and J =-1.38 cm-1 for(2).     

双自由基桥联双铜(Ⅱ)配合物的合成、结构、磁性和分子力学研究

合成和表征了双自由基桥联的双核铜配合物［Ｃｕ（ｈｆａｃ）_２］_２　ＰｈＢＮＭ,其中ｈｆａｃ为 六氟乙酰丙酮负离子,ＰｈＢＮＭ为２,５－二甲基－１,４－二（４,４,５,５－四甲基－３－氧化咪唑啉１－氧 基自由基）苯．配合物的晶体为单斜晶系, Ｃ２／ｃ空间群, ａ＝１．９０１２（４） ｎｍ, ｂ＝１．３７１８（３） ｎｍ, ｃ＝２．１６２ ０（４） ｎｍ,β＝９７．５５（３）°, Ｚ＝４． Ｘ射线衍射结果表明该配合物存在两种构象,其 比例为 ７：３．用分子力学 ＭＭＸ计算了这两种构象的能量分别为 Ｅ_１＝７４０ ｋＪ／ｍｏｌ,Ｅ２＝７７１ ｋＪ／ｍｏｌ．运用不同的自旋多重度作参数,通过ＣＮＤＯ／Ｋ对配合物中磁偶合体系的轨道能 量进行计算,当体系中成单电子为反铁磁偶合时,轨道能量较低,这与磁性测量及其理 论拟合结果一致。     

含烷氧基桥的双核Ni(Ⅱ)配合物的合成、表征和磁性

以Ｎ－氧化吡啶－２－甲醛和１，３－二氨－２－丙醇合成了含烷氧基桥的双Ｓｃｈｉｆ碱双核配体及其五个镍的双核配合物。通过元素分析、摩尔电导、红外光谱、ＴＧ对配合物进行了表征，并对其中两个配合物中Ｎｉ（Ⅱ）－Ｎｉ（Ⅱ）间磁交换作用进行了研究。     

Synthesis and Crystal Structure of Copper(II) Complex with Mixed Bipyridine and 2-Hydroxy-1-naphthaldehyde Ligands

1 INTRODUCTION Galactose oxidase is a monomeric enzyme that catalyzes the stereospecific oxidation of a broad range of primary alcohol substrates and possesses a unique mononuclear copper site essential for catalyzing a two-electron transfer reaction during the oxidation of primary alcohol to corresponding aldehydes[1]. The catalytic reaction is shown in Eq. 1. RCH2OH + O2 RCHO + H2O2 (1) A recent report on the crystal structure of galactose oxidase reveals a unique mo…     

新型二维草酸根桥联配合物 {[Cu(en)~2]~4[KFe(C~2O~4)~3]~4}~n的合成、结构 和磁性

合成了一个新型草酸根桥联的二维配合物{[Cu(en)2]4[KFe(C2O4)3]4}n,并进行了晶体结构测试和磁性研究.晶体结构分析显示:K+离子为罕见的八配位环境,2个C2O42-和2个或1个K+离子长程桥联2个FeⅢ离子,形成一个二维网状的[KFe(C2O4)3]n2n-骨架,[Cu(en)2]2+单元通过(en)N-H…O(C2O4)氢键与[KFe(C2O4)3]n2n-骨架连接.变温磁化率测量表明:FeⅢ与FeⅢ间存在着弱的磁相互作用,J=-0.17cm-1.