Synthesis and Crystal Structure of a Tetranuclear Silver Complex with Bis（diphenylphosphino） amine-dioxide as a Tridentate Ligand

1 INTRODUCTION The coordination chemistry of the nitrogen-contai- ning diphosphine ligand bis(diphenylphosphino)ami- ne (Ph2PNHPPh2) has recently received much atten- tion because the P atoms can bridge metal centers in μ-bonding mode to form bi- or polynuclear complex- es[1~10]. It has been shown that the acidity of N–H proton would promote functionalization on the ligand backbone[4, 5, 11]. Although a few complexes contain- ing deprotonated tridentate Ph2PNPPh2 have been synthesi…     

铜锌超氧化物歧化酶的结构,机理及其模拟研究进展

1938年Mann等首次从牛红血球中分离得到了超氧化物歧化酶(Superoxide Dismutase简称SOD),1969年Mccord等进一步发现了它的生物活性。超氧化物歧化酶的主要功能是催化歧化超氧阴离子自由基O_2~-,O_2~-+O_2~-+2H~+→+O_2+H_2O_2,使细胞免受O_2~-的氧化性损伤,因此,它在防御氧的毒     

不对称四核环状Co3^IIM^II簇合物的磁化学

本文用一种新的方法对三个核环状化合物Co3Fe(mp)4(Hmp)(PBu3^n)3(1) Co4(mp)4(Hmp)(PMe2Ph)3(2)(H2mp=2-巯基苯酚)和Co4(mp)4(PBu3^n)3Cl(MeOH)(3)进行了1。5-300K温度范围的磁性质研究, 即在各向同性海森堡模型的基础上, 用全矩阵对角化方法求自旋态能量本征值, 从而得到化合物的磁化率, 然后用阻尼最小二乘法拟合变温磁化率, 得到磁交换常数。因避免了使用Kambe理论, 无须对化合物进行模型简化处理, 所以得到更多、更准确的磁交换信息。拟合结果显示三个化合物都呈较弱的磁偶合作用。对化合物1得到J1=-3.14cm^-^1, J2=-3.04cm^-^1, J3=2.92cm^-^1和J4=4.08cm^-^1, 对2得到J1=-3.07cm^-^1, J2=-3.19cm^-^1,J3=-0.33cm^-^1和J4=-1.91cm^-^1; 对3得到J1=-4.818cm^-^1,J2=-4.244cm^-^1, J3=-1.164cm^-^1和J4=-2.634cm^-^1, 其中J1和J2代表通过双重μ2-S桥, J3和J4分别代表通过单重和双重μ2-O桥进行的磁交换作用常数。     

乙炔功能化2,2’:6’,2’’-三联吡啶异三核铂-银(金)配合物敏化稀土近红外发光

以二种高量子产率的异三核PtM2(M=Ag,Au)铂-炔-膦配合物为前驱体分别与Ln(hfac)3(H2O)2(Ln=Nd,Er,Yb;hfac=六氟乙酰丙酮)反应得到六种PtM2Ln2异五核稀土加合物,研究了它们在二氯甲烷溶液和固态的发光性能.通过激发PtM2发色团在可见光区的吸收,PtM2Ln2稀土加合物都发射出相应稀土离子的特征近红外发光.     

Structure and Luminescence Property of a Linear Tetranuclear Gold(Ⅰ)-thiolate Complex through Au-Au Interaction

The synthesis,structure and luminescent property of a tetranuclear gold(Ⅰ)complex with doubly bridging diethyldithiocarbamate(Et2dtc)and 1,1-bis(diphenylphosphino)ethene((Ph2P)2C=CH2)are described.The complex crystallizes in monoclinic space group C2/c with a=26.785(7),b=25.654(6),c=12.277(3)A,β=106.879(5)°,V=8073(4)A~3,Z=8,C31H32Au2F6NO3P2S2Sb,Mr=1222.32,Dc=2.011 g/cm~3,F(000)=4592,Rint=0.0529,T=293(2)K,μ=8.157 mm~(-1),the final R=0.0464 and wR=0.1444 for 5804 observed reflections with I2σ(Ⅰ).The intramolecular and intermolecular Au¨Au distances are 2.8670(9)and 3.2367(9)A,respectively.Weak emission appears at 517 nm at room temperature in the solid state.     

草酰胺桥联双核铜配合物结构单元的从头算

运用Gaussian 94W量子化学程序包 ,采用LanL2DZ基组 ,对草酰胺桥联双核铜配 (聚 )合物结构单元Cu2 (oxen) (OH) 2 [H2 oxen =N ,N' 二 ( 2 胺乙基 )草酰胺 ](包括顺、反构型及其单、三重态电子组态 )进行从头算研究 ,探讨该配合物结构单元的稳定性 ,并从电荷布居及分子轨道组成等电子结构特征分析这种配合物反式三重态比较稳定的原因 .计算结果与实验规律相符合 .     

Reaction of sulfur-containing structural units of transition metals

Two tri-n-butylphosphme-participated ( PBu3n) nickel (Ⅱ) complexes of 2-mercaptophenol(H2mp),i.e,Ni2Ru(mp)3(Hmp)(PBu3n)3 3 exhibiting a curved heterotrinuclear metal skeleton and its mononuclear "synthon",[HNEt3] [Ni(mp) (Hmp) (PBu3n)] 1 were synthesized and characterized by X-crystallography and 1H NMR,FAB-MS and cyclic valtammogram measurements.The nickel(Ⅱ) center in 1 has a square-planar geometry For 3,the ruthenium(Ⅲ) atom is in a distorted octahedral environment and the two mckel(Ⅱ) atoms exhibit square-planar and rare triangle-planar geometries,respectively.The Ni (1)-Ru-Ni(2 ) arrangement is severely asymmetric with the distances 0.254 and 0.394 nm,respectively,for Ni(1)-Ru and Ni(2)-Ru.The structural regularities of relevant complexes are summarized in relation to the structural as well as spectra data.     

含硫过渡金属基元的反应Ⅱ.双膦及双齿巯基混合配位钴,镍化合物的合成和结构特征

双膦(P^P)和1,2-双齿巯基(S^X)混合与MCl2(M=Co,Ni)反应,得到通式为M(S^X)(P^P)的产物.晶体结构测定表明,配合物Co(bdt)(dppe)(1),Ni(tdt)(dppm)(2)和Ni(tsal)(dppe)(3)中的金属均为SXP2配位的四方平面构型,S,X,P原子分别来自二种双齿配体,各形成四、五或六元螯合配位环.文中总结了结构特征,探讨了基元配合物稳定的原因.     

Synthesis and Crystal Structure of Bis-(2,2'''' bipyridyl)-2-pyrimidinethiolate-Ni(Ⅱ) Complex

1 INTRODUCTION The design of metal complexes of bipyridine is one of the most highlighting topics in molecular materials with specific optical, electronic and mag- netic properties. What studied and well-documented most widely are those of the d6 metal polypyridines, and so are the d8 and d10 metal complexes with rich luminescence behaviour[1] very recently, which can be beneficial to the design of unique functional ma- terials. Currently our interest is to design lumine- scent heteronuc…