铜(Ⅱ)与N(2-羟基乙基)水杨醛亚胺配合物的合成、结构和热分解

人们在探索新的有效抗癌药物时,发现了一些Schiff碱及其和某些金属生成的配合物具有抗癌作用^[1,2]。为研究此类配合物的抗癌作用和结构的关系,我们合成了一系列Schiff碱类配合物^[3,4]。     

不对称双席夫碱Cu(II)同双核及Cu(II)-Mg(II)- Cu(II)异三核配合物的合成与晶体结构

近年来的研究表明，某些过渡金属Schiff碱配合物具有抗菌、抗癌、抗病毒活性。不对称Schiff碱配合物因其特殊的结构和性质正日益受到人们的关注^[3]。但由于不对称双Schiff碱及其配合物的合成及单晶培养比较困难，国内有关其合成与结构的报道较少。我们曾首次合成了不对称双Schiff碱配合物HCuL (H₃L为N-3-羧基水杨醛-N^/-水杨醛-缩乙二胺)及其多个异三核配合物^[1，2]，本文报道的是该系列同双核配合物(HCuL)₂(1) 及Cu(II)-Mg(II)-Cu(II)异三核配合物（2），并通过X-射线衍射的方法解析了两个配合物的晶体结构。配合物1的晶体属单斜晶系，Cc空间群，晶胞参数为a=2.5326(5)nm, b=0.88861(18)nm, c=1.3738(3)nm, β =96.95(3)°, Z=4, R1=0.0520,wR2=0.0968, 此配合物是两个HCuL分子通过酚氧桥联而形成的双聚分子。配合物2的晶体属单斜晶系， Pc空间群，晶胞参数为a= 1.1816(2)nm, b=1.5599(3)nm, c=1.9642(4)nm, β =98.22°, Z=2, R1=0.0701,wR2=0.1498，其晶格的每个不对称单元包含两个异三核中性分子[CuL(H₂O)]Mg[CuL(CH₃OH)]}和{[CuL]Mg[CuL(H₂O)]}     

Shiff碱茚(1,2-b)喹喔啉-11-酮缩氨基硫脲合钴髤配合物的合成、表征与晶体结构

0引言腙类Schiff碱及其配合物,由于具有光、电、磁性质和一定的抗菌、抗癌等生理活性作用一直是人们关注的热点[1￣3]。其中缩氨基硫脲Schiff碱及其配合物由于其不仅是性能优良的有机显色剂,而且还具有抗菌、抗病毒等生物活性,同时也是研究生物催化作用的模版,因而被广泛研究[4]。茚(1,2鄄b)喹喔啉鄄11鄄酮衍生物是一类重要的含N杂环,最近的研究显示其具有一些相当有趣的性质[5],然而有关其合成Schiff碱的研究很少,迄今为止,相关文献只有3例[6￣8],并且未见任何单体或配合物的单晶结构报道。此外,目前的Schiff碱结构中,大多是从芳环外羰基…     

双吡啶酰腙Schiff碱HgⅡ/Cd(Ⅱ)配合物的合成及其对甲醇蒸气的吸附

合成了双吡啶酰腙Schiff碱配体(L),并采用核磁共振氢谱、质谱、红外光谱和元素分析等手段对其结构进行了表征。进一步采用溶剂挥发法合成了2个配合物{[Cd(L)_2Cl_2]·2DMF·6H_2O}n (1)和[Hg(L)Cl_2]n (2)。通过X射线单晶衍射技术测定了配体及2个配合物的单晶结构,并对配合物的热稳定性及其在常温下对甲醇蒸气的吸附进行了考察。实验结果表明,2个配合物均为1D配位聚合物,配合物1对甲醇蒸气有较好的吸附能力。     

5-硝基水杨醛缩硫脲及其铜(Ⅱ)、镍(Ⅱ)、锌(Ⅱ)配合物的合成与光热性质

用5-硝基水杨醛与硫脲缩合制备出一种Schiff碱配体,将其分别与Cu(Ⅱ),Zn(Ⅱ)和Ni(Ⅱ)作用合成出了Schiff碱配合物.采用元素分析、红外光谱、紫外光谱、差热热重、摩尔电导率、核磁共振等分析方法对化合物进行表征和测试,并研究了配合物的热力学稳定性及其荧光性质.     

Schiff碱配合物Cd(H2SalN)2(OAc)2(H2O)]·3(H2O)的合成与结构

用一步法合成了一个Schiff碱配合物[Cd(H2SalN)2(OAc)2(H2O)]·3(H2O)(H2SalN=salicylaldehyde isonicotinoylhydrazone),并用IR和X射线单晶衍射进行了结构测定.该化合物属于三斜晶系,P-1空间群,晶胞参数为:a =1.554 4(3) nm,b...     

双吡啶酰腙Schiff碱双核Fe(Ⅱ)配合物的合成与磁性

基于己二酰肼双缩(溴代)吡啶甲醛Schiff碱配体HLx(x=1,2),合成了2例双核Fe(Ⅱ)配合物,并通过红外光谱、X射线单晶衍射分析及磁化率测量等手段对配合物进行了表征。X射线单晶衍射分析结果表明,每个独立单元中均含有2个Fe(Ⅱ)离子、2个配体单元和4个高氯酸根阴离子,Fe(Ⅱ)离子呈N4O2八面体配位构型。分子间π…π堆积作用将配阳离子连成超分子一维链结构。磁性测试表明2个配合物都是高自旋态,同时配合物2呈现弱的分子间铁磁耦合作用。     

N-(2-氧乙酸-3-甲氧基)苄叉二胺合锌(Ⅱ)配合物的合成、晶体结构及光学性质研究

本文通过修饰邻香草醛芳环上羟基的方法,得到两种Schiff碱配体:N,N′-二(2-氧乙酸-3-甲氧基)苄叉乙二胺(H2L1)和N,N′-二(2-氧乙酸-3-甲氧基)苄叉1,3-丙二胺(H2L2),利用水热合成方法以新合成的配体为基点设计合成了2个新的六配位Schiff碱锌(Ⅱ)配合物[Zn(L1)]·7H2O(1)和[Zn(L2)]·7H2O(2),通过元素分析、红外光谱和核磁共振光谱等测试手段对配合物进行了表征,并用X射线单晶衍射测得Zn(Ⅱ)配合物的晶体结构。X射线晶体学研究表明两种配合物晶体结构中都包含多个溶剂水分子,配合物1是以Zn(Ⅱ)为中心扭曲的三方棱柱构型,配合物2是以Zn(Ⅱ)为中心扭曲的八面体构型。初步研究了两种配合物的固体发光性,结果表明这两种配合物具有良好的光致发光的性能,有望在光学材料方面得到应用。     

4-(3H)-喹唑酮Co(Ⅱ)、Ag(Ⅰ)配合物的合成、晶体结构、荧光和抗癌活性

以4(3H)-喹唑酮、Co(NO3)2·6H2O、Ag NO3为原料,在相同物料比、溶剂和常温条件下,合成了配合物[Co(L)2·(H2O)2·(NO3)2](1)和[Ag(L)2·(NO3)](2)(L=4-(3H)-喹唑酮)。对其进行了X-射线单晶衍射表征和热重分析。X-射线单晶衍射分析表明,它们都属于三斜晶系,但1是六配位,2是三配位的。还测定了2的固体荧光和抗癌活性。配合物2的最大发射波长比配体红移了27 nm,其对NCI(人非小细胞肺癌细胞)有较好的抗癌作用。     

配合物[M(AAABA)2(py)2(H2O)2，M=Zn、Mn]的合成、晶体结构、荧光性质和理论研究

合成了乙酰丙酮缩邻氨基苯甲酸Schiff碱(HAAABA)(HAAABA=acetylacetone-o-aminobenzoic acid),获得了其锌和锰的配合物单晶[M(AAABA)2(py)2(H2O)2,M=Zn,1;Mn,21.产物经IR、核磁共振谱、元素分析、X-射线单晶结构分析等表征.两晶体均属于单斜晶系,空间群为P21/m.用Guassian 03W程序,在B3LYP/6-31G等水平上对标题化合物进行了几何全优化,并对其成键情况、自然键轨道(NBO)及键能进行了分析.在DMF中测定了Schiff碱配体及其锌配合物的荧光性质.     

PHOTOLYSIS OF AQUEOUS SOLUTIONS OF POTASSIUM CIS-DIAQUOBIS (OXALATO) CHROMATE (III)

Abstract— The photolysis of aqueous solutions of cis -[Cr(C₂O₄)₂(H₂O)₂]- at 254 nm and pH 4 produced CO₂ and H₂ in nearly equal yields. The quantum yield of hydrogen, φ², increased by 9% and the yield of carbon dioxide, φ, by 65% as the pH was lowered from 4 to I. The total gas yield, φ_gas, decreased in the presence of added oxalate or chromium (II) ions and when the light intensity was lowered. The gas yield in D₂O was appreciably higher than in H₂O. The variation of φ_gas with pH (D) and with added oxalate ion was roughly parallel in the two liquid media. The gas yield increased in the series:
A tentative mechanism is suggested to explain the results.     

CRYSTAL STRUCTURES OF COPPER (Ⅱ) AND COBALT (Ⅲ) COM- PLEXES OF o-HYDROXYBENZYLGLYCINATE (HBG)

<正> The structures of two complexes C(CuOC6H4CH2NHCH2COO)2 (H2 O)]·H2P(1) and [Co(NH3)6[Co(OC6H4CH2NHCH2COO)2]2[C1]·10H2O (2) were determined by X-ray analyses. Compound (1) crystallizes in the orthorhombic space group P212121 with a=11. 357(1),b= 24. 304(2),c=7.317(4) A,Z= 4;While compound (2) in the monoclinic space group A2/a(C2/c) with a=23. 486(9) ,b=26. 605(6) ,c= 10. 542(1) A,γ= 128. 42(4)°,Z= 4. In compound (1),two Cu(Ⅱ) ions are bonded together by the phenolic oxygen atoms of two tridentate chelating ligands and each of them is separately coordinated by the carboxyl oxygen,amino nitrogen of each chelate ligand and by the fifth oxygen atom as well (from aqua or the carbonyl group in adjacent molecule). Thus the coordination of each Cu(Ⅱ) is a square pyramid with distances of 1. 93- 1. 97A to the four corner atoms and 2. 30 and 2. 32 A to the apex atoms. The whole molecule has an approximately planar configuratioir with the two pyramid apexes pointing towards one side. Compound (2) consists of     

MOLECULAR STRUCTURE OF (BENZOPHENONE)BIS(TRICARBONYLCHROMIUM)

<正> The title crystal belongs to monoclinic system, space group P21/c, with 3=14.794(2), b=7.360(1), c=16.029(2) A, β=94.95(2)0, Z=4, V=1738.9(6)A3, Dx=1.735 g/cm3. The final R=0.047, Rw=0.052.     

INFRARED ASSIGNMENT OF BIS(GLYCOLATO)-BIS(PYRIDINE) METAL(II) COMPOUNDS AND CRYSTAL STRUCTURE OF TRANS-BIS(GLYCOLATO)-CIS-BIS(PYRIDINE)NICKEL(II) DIHYDRATE

Abstract

Infrared spectra of the coordination compounds [MG₂(py)₂], M(II)=Co, Ni, Cu and Zn; G=glycolato, py=pyridine, have been fully assigned by means of py and py-d ₅ and glycolato α—OH and α—OD (G-d) labelling as well as metal ion substitution in the 4000–70cm^?1 region. The crystal structure of the Ni(II) compound is presented and the spectra of the compounds are discussed on the basis of their structure and their bonding to the glycolato and pyridine ligands. Vibrational frequencies obtained for the Ni(II) compound are compared to those obtained by calculations carried out using the Gaussian 94 program package.     

KINETICS OF THE CHROMIUM(II) REDUCTIONS OF CHELATED AMINO ACIDO-BIS(ETHYLENE-DIAMINE)COBALT(III) COMPLEXES

Abstract

The kinetics of Cr²⁺(aq) reductions of glycinato-, D,L-alanato, D,L-phenylalanato-, and D,L-leucinatobis-(ethylenediamine)cobalt(III) ions have been investigated. The rate law is of the form d(ln[Co(III)]/dt = k[Cr²⁺], where the rate constant k(M^?1sec^?1) and associated activation parameters δH^δ(kcal mol^?1 and δS^δ (cal deg ^?1mol^?1) in parentheses, are respectively 1.65 · 0.06 (9.7 · 0.1, -25 · 1), 0.367 · 0.008 (10.9 · 04,-24 ·1), 0.529 · 0.021 (11.2 · 0.4, -22 · 1); and 0.358 · 0.019 (11.5 · 0.3, -22 · 1) at 298^·K and ·[CIO·] = 1.0 M. The reactions are all inner-sphere.     

四(邻N-甲基烟酰胺基)苯卟啉与Cu(Ⅱ)的反应动力学研究

在20.0±0.1℃,0.1M KCl介质及乙酸或丁二酸缓冲条件下,研究了水溶性的四(邻N—甲基烟酰胺基)苯卟啉(H_2-TM(O-Nic)PP)与Cu(Ⅱ)的反应动力学。实验结果表明,Cu(Ⅱ)嵌入H_2-TM(O-Nic)PP的反应速率对卟啉是一级反应。表观一级速率常数表达式如下:对Cu(Ⅱ)-酸盐体系,其中,对Cu(Ⅱ)-丁二酸盐体系,其中,提出了Cu(Ⅱ)嵌入H_2-TM(O-Nic)PP的反应机理,并对乙酸缓冲体系和丁二酸缓冲体系中反应动力学的差别作出了讨论。     

三(对-甲苯磺酰氧甲基)硝基甲烷的还原和N-三(对-甲苯磺酰氧甲基)甲基羟氨的空气氧化

三(对-甲苯磺酰氧甲基)硝基甲烷(1)于苯中,以锌粉和醋酸在加或不加醋酸酐下可以被还原,并分別形成相应的羟氨(2)或其醋酸酯(3)。值得注意的是,当2和3以1M甲醇钠在氯仿中处理时,受空气氧化后又形成硝基化合物(1),但在排除空气时,不发生这一氧化反应。同样,三(苯甲酰氧甲基)硝基甲烷当用锌粉-醋酸还原时可生成相应的胺。     

STRUCTURES OF PYRIDINE CARBOXYLATE COMPLEXES OF COBALT(II) AND COPPER(II)

Abstract

The syntheses and crystal structures of [Co(nic)₂(H₂O)₄] (1). [Co(iso)₂(H₂O)₄] (2). [Cu(nic)₂(H₂O)₄] (3), and [Cu(iso)₂(H₂O)₄] (4) (nic = nicotinate; iso = isonicotinate) are reported. Complex 1 crystallizes in monoclinic, space group C2/m with cell parameters a =14.150(4). b = 6.883(2)., c = 8.497(2) Å, β= 118.28(2)° and Z = 2. The other crystals. 2. 3. and 4. are all triclinic, Pī; a = 9.777(3), b = 6.348(4), c = 6.888(3)Å, a= 113.10(6)., β= 110.55(3). γ = 97.61(5)°, and Z=l for 2; a = 7.0281(4), b = 7.7176(6), c = 8.6978(7)Å, a = 68.103(7), β = 68.526(5), γ = 62.550(6)°, and Z=1 for 3; a = 9.1807(4), b = 6.3334(3), c = 6.8871(3)Å, a= 108.213(4), β = 99.433(4), γ= 105.190(4)°, and Z= 1 for 4. The arrangements around the metal ions are trans-octahedra with two pyridyl nitrogens and two aqua oxygens in the equatorial positions and two aqua oxygens in the axial positions, although the Cu(II) complexes show a larger Jahn-Teller distortion.     

STEREOCHEMISTRY OF (R)-2-METHYLAZIRIDINE COMPLEXES OF COBALT(III) AND DIMERIZATION OF THE LIGAND

Abstract

A cobalt(III) complex containing (R)-2-methylaziridine (R-meaz), [Co(R-meaz)(NH₃)₅]³⁺, was prepared and the two diastereomers arising from the presence of the chiral nitrogen atom (N(R) and N(S)) were separated by column chromatography. Molecular mechanics calculations estimated the N(R)-isomer to be more stable. This result was supported by the x-ray structure determination of the more abundant (ca. 94%) isomer, N(R)-[Co(R-meaz)(NH₃)₅]Br₃H₂O. Crystal data: monoclinic, P2₁, a = 7.357(1), b = 9.780(1), c = 10.426(1) Å, μ = 93.58(1)°, V= 748.7(3) ų, Z= 2. Kinetic studies of isomerization (epimerization) between the two isomers revealed that inversion at the nitrogen center was very slow (5 × 10^?2 M^?1 S^?1at 25 °C). The small rate constant seems to be related to the strained three-membered structure of the meaz ligand. The reaction of Na₃[Co(N0₂)6] and R-meaz yielded a complex containing two dimerized R-meaz chelates, trans-[Co(NO₂)2(di-R-meaz)₂] (di-R-meaz =RR)-α,2-dimethyl-l-aziridineethanamine). The crystal strucrure of trans-[Co(NO₂)₂ (di-R-meaz)₂]C1O₄H₂O was established by x-ray crystallography. Crystal data: orthorhombic, P2₁2₁2₁, a = 11.784(6), b = 21.023(9), c = 8.608(7) Å, V = 2133(2) ų, Z = 4.     

铁(Ⅲ)离子在ATP与去铁转铁蛋白之间交换动力学的研究

使用分光光度法研究了Fe(Ⅲ)离子在去铁转铁蛋白(apoTf)与ATP之间的交换动力学,得到反应的动力学参数及反应速率表达式,并提出了反应机理。