瑞香素稀土配合物的合成和性质

自六十年代以来陆续发现稀土化合物具有一系列特殊的药效作用 ,使稀土元素在药物上的应用展现出广阔前景。目前 ,已有不少稀土化合物应用于临床 ,如抗凝血药物 3 磺酸异烟酸钕、左旋糖酸镨、钕混合物 ;消炎药水杨酸钐等。合成具有生物活性配体的稀土配合物是寻找有效稀土药物的一条途径。瑞香素是一具有抗菌、抗炎、抗凝血等生物活性的香豆素类化合物 ,其分子结构为 :稀土与香豆素类的配合物的合成与性质研究己有不少报道[1,2 ] 。为了进一步研究这类配合物的性质和生物活性 ,我们合成了六种瑞香素稀土配合物。1　实验部分1 .1　仪器及试剂…     

Solvothermal Synthesis, Crystal Structure and Electrochemical Property of Complex [Co(p-MBA)2(2,2''-bipy)(H2O)]·(H2O)

One novel complex [Co(p-MBA)2(2,2'-bipy)(H2O)]·(H2O) has been synthesized by the reaction of p-methylbenzoic acid with 2,2'-bipyridine in the solvent mixture of water and methanol. It crystallizes in triclinic, space group P-1 with a=0.70479(14), b=1.1211(2), c=1.6718(3) nm, α=103.806(3), β=90.795(3), γ=104.207(3)°, V=1.2399(4) nm3, Mr=512.41, Dc=1.373 g/cm3, Z=2, F(000)=532, μ=0.733 mm-1, R=0.0432 and wR=0.0957. The crystal structural analysis shows that the cobalt atom is coordinated with three oxygen atoms from two p-methylbenzoic acids and one water molecule and two nitrogen atoms from one 2,2'-bipyridine,forming a distorted square-pyramidal coordination geometry. The cyclic voltammetry behavior of the complex is also reported.     

固相配位化学反应研究——ⅩⅩⅩⅩⅠ.[Co(NH_3)_5(H_2O)]Br_3,[Cr(NH_3)_5(H_2O)](NO_3)_3与无机盐KY(Y=Cl,Br,Ⅰ)的固相反应动力学研究

本文主要用气相色谱逸出气体分析方法,借助于红外、紫外可见漫反射谱等手段研究了[Co(NH_3)_5(H_2O)]Br_3、[Cr(NH_3)_5(H_2O)](NO_3)_3与无机盐KY(Y=Cl,Br,Ⅰ)的固相反应,计算了失水与失氨的动力学参数,发现第一步反应失水生成一取代中间产物,其活化能与外加阴离子无关,为S_N1过程。第二步失氨反应活化能与中心离子M以及取代基Y有关,当M=Co(Ⅲ)时,反应体系的失氨活化能大小有下列顺序:Cl>Br>Ⅰ(E值分别为187、155、98kJ·mol~(-1)),M=Cr(Ⅲ)时则正好相反:Ⅰ>Br>Cl(E值分别为213、146、79 kJ·mol~(-1))。     

Synthesis,Structure and Photoluminescence of Co-crystal of Bis[2-(benz(oxa/imida)zol-2-yl)phenolato-κ2N,O]zinc(Ⅱ) Being Site Occupancy Disorder with a Heteroatom Ratio of NH to O (0.408/0.592)

The zinc(Ⅱ) complex with Hpbx (Hpbx = 2-(benzoxazol-2-yl)phenol) and Hpbm (Hpbm=2-(benzimidazol-2-yl)phenol),namely[Zn(pbm)2]1.633[Zn(bpx)2]2.367·DMF·2H2O1,has been synthesized and characterized by X-ray crystallography,FTIR and elemental analysis.The coordination structures are statistically disordered and can be regarded as a co-crystal of [Zn(pbm)2]and [Zn(pbx)2] with the ratio of ca.0.408/0.592.Solvate water and DMF molecules are also present in the lattice.Crystal data for 1:monoclinic,space group P21/c,Mr= 2049.02,Z = 2,α = 9,7571(6),b = 25.6415(16),c = 19.8675(10)(A),β = 111.342(2)°,V = 4629.7(5) (A)3,Dc = 1.470 g/cm3,μ =1.100 mm-1,F(000) = 2104,R = 0.0575 and wR = 0.1282 for 5528 observed reflections (I＞ 2σ(I)).The photoluminescent spectra for this compound have also been studied.     

Synthesis and Crystal Structure of [{Cd(hmbdc)(H2O)3}·2H2O]n

A novel coordination polymer [{Cd(hmbdc)(H2O)3}·2H2O]n (hmbdc=5-hydroxy- isophthalic acid) has been synthesized and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c, with a=9.599(3), b=18.699(5), c=7.557(2) (A), β= 108.198(4)°, V=1288.6(6) (A)3, Z=4, Mr=382.60, Dc=1.972 g/cm3, F(000)=760, μ=1.740, the final R=0.0555 and wR=0.0995 for 1732 observed reflections with Ⅰ ＞ 2σ(Ⅰ). The structural analysis shows that the intermolecular hydrogen bonds and π-π interactions result in a three-dimensional supramolecular framework.     

Dynamic stereochemistry of hypervalent silicon, germanium and tin compounds containing amidomethyl C, O-chelating ligands

The results of NMR-spectroscopy studies of the structure, dynamic stereochemistry, and intermolecular interactions in solutions of organic derivatives of penta-and hexacoordinated silicon, germanium, and tin containing amidomethyl, lactamomethyl, and related bidentate ligands are surveyed. For the series of works “Dynamic stereochemistry of hypervalent compounds of silicon, germanium, and tin,” the author was awarded the Academia Europea Prize for young scientists from CIS in 1996. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1912–1934. November, 1997.     

Structure of Sol-Gel-Derived Sodium Dititanate Glass

The sodium dititanate, Na₂O·2TiO₂ glass was prepared by the sol-gel method. The structure of the glass, especially local environment of Ti⁴⁺ ions was examined using X-ray diffraction and X-ray absorption fine structure (XAFS) analyses, and was compared with that of the melt-derived glass with the same composition. It was found that Ti⁴⁺ ions are rather in five-fold coordination state, forming TiO₅ pyramids with one doubly bonded Ti=O in the gel-glass, while they were in lower coordination state or four-fold coordination in the melt-derived glass.     

Structural assignment of organotin hydrides containing the oxazoline ligand

A series of triorganotin hydrides and diorganotin dihydrides containing the optically active 2-(4-isopropyl-2-oxazolinyl)-5-phenyl ligand have been characterized by means of the multinuclear low-temperature NMR investigations, the results of which are discussed. In the corresponding organotin hydrides values of the ¹J(¹H-^117/119Sn) couplings appeared to be temperature dependent, supporting an axial/equatorial position of the hydrogen attached to the tin.     

配合物Cu_2（C_（21）H_（20）N_2O_3）（CH_3COO）_2的EXAFS研究

用延伸Ｘ射线吸收精细结构（ＥＸＡＦＳ），测定了标题化合物中两个铜原子的配位结构。两个铜原子有相同的配位，确认每个铜原子均与一个氮原子，三个氧原子形成四配位结构。一氧一氮源于ＨＳＢ，而另两个氧由乙酸提供。     

One‐Dimensional,Cofacial Porphyrin Polymers Formed by Self‐Assembly of meso‐Tetrakis(ERE Donor) Zinc(II) Porphyrins

A series of meso‐tetrakis‐(ERE donor) zinc(II) porphyrins n Zn (ERE donor=4‐R‐3,5‐bis[(E)‐methyl]phenyl; 1 Zn: E=NMe₂, R=Br; 2 Zn: E=NMe₂, R=H; 3 Zn: E=OMe, R=Br; 4 Zn: E=OMe, R=H) have been synthesized in excellent yields. As a result of the combination of a Lewis acidic site and eight Lewis basic sites within one molecule, monomeric molecules of n Zn self‐assemble to form one‐dimensional porphyrin polymers [ n Zn]_∞ in the solid state, as confirmed for 1 Zn and 3 Zn by X‐ray crystallography. The coordination environment around the zinc(II) ions in these polymers is octahedral. They are ligated by four equatorial nitrogen atoms of the porphyrin and two apical E atoms (E=N, O) provided by the EBrE donor groups of adjacent n Zn molecules. Complexes 2 Zn and 4 Zn did not form single crystals, but solid‐state UV/Vis analysis points to the formation of similar structures. Solution UV/Vis and ¹H NMR spectroscopy indicated that interactions between 1 Zn and 2 Zn monomers in the polymers are stronger than between 3 Zn and 4 Zn monomers. Interestingly, they also revealed that the presence of a neighboring bromine atom in the EBrE donor groups has a considerable influence on the coordination properties of the benzylic N or O atoms. The zinc(II) ions of the porphyrins most likely adopt only hexacoordination in the solid state, owing to the unique predisposition of Lewis acidic and basic sites in the n Zn molecules. Several parameters of the aggregates, for example, the interplanar separation between porphyrins and the zinc–zinc distances, change as a function of the coordinating E groups. The high degree of modularity in their synthesis makes these zinc(II) porphyrins an interesting new entry in noncovalent multiporphyrin assemblies.