水杨醛及邻香草醛缩丙醇胺与锰形成的配合物的合成与红外光谱

锰的配位化学由于其生物功能,而愈来愈引起人们的广泛兴趣。在某些生物酶中,锰的配位环境多为咪唑的氮和羧基及水分子的氧原子配位［１,２］。由于Ｓｃｈｉｆ碱以氮原子和氧原子配位,与生物环境接近,在模型配合物研究方面,以多齿Ｓｃｈｉｆ碱为配体的锰的配合物,特...     

2—氨基噻唑缩水杨醛合Zn（Ⅱ）配合物的合成,表征及抑菌活性

２－氨基噻唑缩水杨醛合Ｚｎ（Ⅱ）配合物的合成、表征及抑菌活性梁芳珍郝京诚黄汝骐（山东师范大学化学系济南２５００１４）众多的Ｓｃｈｉｆ碱及其金属配合物以其良好的抑菌、抗癌和抗病毒的生物活性［１］，一直受到人们的重视。含硫Ｓｃｈｉｆ碱是其中有影响的一类，...     

铱(Ⅰ)/铑(Ⅰ)联萘胺Schiff碱(BPMBNDI)络合物催化的不对称氢转移反应研究

铱（Ⅰ）／铑（Ⅰ）联萘胺Ｓｃｈｉｆ碱（ＢＰＭＢＮＤＩ）络合物催化的不对称氢转移反应研究自国甫尹承烈＊（北京师范大学化学系１００８７５）近年来，一些含氮手性配体的过渡金属催化剂在均相不对称氢硅烷化反应和不对称氢转移反应中已获得广泛应用［１］。在这两类反...     

Co(Ⅱ)、Mn(Ⅱ)Schiff碱配合物的合成及其对超氧离子的抑制作用

Ｓｃｈｉｆｆ碱及其金属配合物具有抗菌、抗癌等生物活性［１］,尤其是钴（Ⅱ）Ｓｃｈｉｆｆ碱配合物具有催化及可逆载氧等特殊性能［２］,引起人们极大的研究兴趣。本文合成了四种新型的未见文献报道的Ｃｏ（Ⅱ）、Ｍｎ（Ⅱ）Ｓｃｈｉｆｆ碱配合物。研究表明这类配合物结构稳定、生物活性高,可作超氧化物歧化酶的模拟物,对超氧离子Ｏ２-自由基有良好的催化歧化作用。１实验部分１１配体（５氯水杨醛缩盐酸氨基脲ＨＬ）的合成将等摩尔的自制５氯水杨醛［３］（３１３ｇ）的乙醇液滴加于盐酸氨基脲（２２３ｇ）的中性水溶液中,在８６℃的恒…     

邻香草醛缩氨基酸钾Schiff碱及其三苄基锡(Ⅳ)配合物的合成与表征

有机锡配合物具有明显的抗肿瘤活性,已引起化学工作者的研究兴趣［１］。鉴于三苄基氯化铝（Ⅳ）是一种原料易得、易合成、毒性小的有机锡化合物;邻香草醛缩氨基酸钾Ｓｃｈｉｆｆ碱是一类具有重要意义的生物活性配体,两者形成的配合物,有可能表现更典型的生物活性。某些邻香草醛缩氨基酸Ｓｃｈｉｆｆ碱与过渡金属形成的配合物已有报道［２,３］,但邻香草醛缩氨基酸钾Ｓｃｈｉｆｆ碱及其三苄基锡（Ⅳ）配合物尚未见报道,因此,本文合成六种邻香草醛缩氨基酸钾Ｓｃｈｉｆｆ碱及其配合物,通过元素分析、ＩＲ、ＵＶ、１ＨＮＭＲ等物理化…     

3,5—二溴水杨醛Schiff碱的铜（Ⅱ）配合物研究

３，５－二溴水杨醛Ｓｃｈｉｆ碱的铜（Ⅱ）配合物研究赵全芹柳翠英王德凤于爱华（山东医科大学药学系济南２５００１２）关键词３，５－二溴水杨醛Ｓｃｈｉｆ碱配合物抑菌活性中图分类号Ｏ６１４．１２１Ｓｃｈｉｆ碱衍生物与过渡金属离子所形成的配合物具有抗癌、抗病毒...     

β－烷氧羰乙基三氯化锡与水杨醛缩苯胺类Schif碱配合物的合成及表征

由β－烷氧羰乙基三氯化锡与水杨醛缩苯胺类Ｓｃｈｉｆ碱反应，合成了１３种新的有机锡－Ｓｃｈｉｆ碱配合物。经元素分析、ＩＲ、ＮＭＲ和ＴＧ－ＤＳＣ测定，对其结构进行了表征，配合物是通过酚羟基氧原子和锡原子的配键生成的。摩尔电导率测定结果表明，配合物均为非电解质。     

冠醚化对双Schiff碱钴（Ⅱ）配合物催化氧化性能的影响

合成了冠醚化钴（Ⅱ）Ｓｃｈｉｆ碱配合物１ｃ及其相关类似物１ｂ，测定了它们的氧加合常数，考查了它们对异丙苯的催化氧化性能，并与未冠醚化的类似物１ａ作比较，讨论了１ｃ分子中的冠环对催化氧化性能的影响     

双[N,N‘—1,2—亚乙基—2,2’—（苯基亚甲基）二（3,4—二甲基吡？…

首次报道了一个新的拟酶模型物－双［Ｎ，Ｎ＇－１，２－亚乙基－２，２＇－（苯基亚甲基）二（３，４－二甲基吡咯－５－醋缩亚胺）］合双锰的合成方法及光谱特征；并对用ＰｈＩＯ单加氧化环己烷反应的催化性能及自氧化反应进行了研究。结果表明，此Ｓｃｈｉｆｆ碱双锰配合物的催化性能及稳定性与金属卟啉ＴＰＰＭｎＣｌ相似。     

有机硅聚合物负载硫、腈钯(0)配合物催化丙烯酸衍生物芳基化的研究

钯催化下共轭烯烃的Ｈｅｃｋ芳基化是立体选择性形成碳碳键的重要方法,在有机合成中广为应用［１］．均相钯催化剂因难以从反应体系中分离回收,其实际应用受到限制．聚合物负载过渡金属催化剂因综合了均相和复相催化过程的优势,已越来越引起人们的关注,聚苯乙烯负载的膦钯配合物能有效地催化共轭烯烃的芳基化［２,３］．Ｚｈａｎｇ等报道了聚合物负载菲咯啉钯（０）配合物催化丙烯酰胺的芳基化［４］,但该催化剂的制备过程过于复杂．作者曾报道过聚γ巯丙基硅氧烷钯（０）配合物的合成,并证实其是苯乙烯、丙烯酸Ｈｅｃｋ芳基化反…     

氮杂冠醚化双Schiff碱配合物催化羧酸酯水解的研究

将4种氮杂冠醚取代的双Schiff碱钴(H)、锰(m)配合物作为仿水解酶模型催化羧酸酯(PNPP)水解.考察了Schiff碱配合物中氮杂冠醚取代的位置、氮杂冠醚的数目对其仿水解酶性能的影响;探讨了Schiff配合物催化PNPP水解的动力学和机理;提出了配合物催化PNPP水解的动力学模型.结果表明,在25℃条件下随着缓冲溶液pH值的增大,配合物催化PNPP水解速率提高;四种氮杂冠醚取代的双Schiff碱配合物在催化PNPP水解反应中表现出良好的催化活性;氮杂冠醚3-取代的Schiff碱配合物CoL2的催化活性高于5-取代的Schiff碱配合物CoL1,含有2个氮杂冠醚的配合物CoL3的催化活性高于含有1个氮杂冠醚的配合物CoL2.     

A new class of ruthenium complexes containing Schiff base ligands as promising catalysts for atom transfer radical polymerization and ring opening metathesis polymerization

A novel series of Schiff base ruthenium complexes that are active catalysts in the field of atom transfer radical polymerization (ATRP), have been prepared. Moreover, when activated with trimethylsilyldiazomethane (TMSD), these species exhibit good catalytic activity in the ring opening metathesis polymerization (ROMP) of norbornene and cyclooctene. The activity for both the ROMP and ATRP reaction is dependent on the steric bulk and electron donating ability of the Schiff base ligand. The control over polymerization in ATRP was verified for the two substrates that exhibit the highest activity, namely MMA and styrene. The results show that the optimal ATRP equilibrium leading to a controlled polymerization, can be established by adjusting the steric and electronic properties of the Schiff base ligand.     

Catalytic Kinetics of the Schiff Base Metal Complexes Bearing Side Chain of Cyclic morpholine in Carboxylic Ester Hydrolysis

It has been reported that two Schiff base transition metal complexes bearing the side chain of the morpholine ring were synthesized and characterized, and two complexes with the same base agent but different metal ions were used as a simulant hydrolase in the catalytic hydrolysis of p-nitrophenyl picolinate in this paper. The mechanism of PNPP catalytic hydrolysis is proposed and supported by the results of the spectral analysis and the kinetic calculation. A kinetic mathematical model, applied to the calculation of the kinetic and thermodynamics parameters of PNPP catalytic hydrolysis, has been established on the foundation of the mechanism proposed. The result of the study shows that the two complexes have a good catalytic activity in PNPP catalytic hydrolysis, and the rate of the PNPP catalytic hydrolysis was increased with the increase of the pH values in the buffer solution and affected by the polarization effect of metal ion of the complexes.     

氮杂冠醚取代非对称双Schiff碱配合物催化氧化对二甲苯研究

将一系列苯并-10-氮杂-15-冠-5或吗啉基取代的不对称双Schiff碱配合物作为催化剂,在常压和120℃条件下用于催化氧化对二甲苯研究。探讨了Schiff配合物中心金属离子、Schiff碱配体中挂接的氮杂冠醚环、配体芳环上取代基等对催化氧化对二甲苯反应活性及其氧化产物选择性的影响。实验结果表明:配合物中氮杂冠醚的存在能显著缩短反应诱导期、提高催化活性和选择性;Schiff碱Mn(Ⅲ)配合物比Schiff碱Co(Ⅱ)和Schiff碱Cu(Ⅱ)具有更高的催化活性;氮杂冠醚Schiff碱Mn(Ⅲ)配合物催化氧化二甲苯的转化率和产物选择性分别达75%和90%。     

氮杂冠醚取代单Schiff碱过渡金属配合物催化氧化对二甲苯研究

本文将苯并-10-氮杂-15-冠-5或吗啉基取代的单Schiff碱过渡配合物作为催化剂,在常压和120℃条件下,以空气为氧源,研究了对二甲苯催化氧化反应。实验探讨了Schiff碱配合物中心金属离子、Schiff碱配体中挂接的氮杂冠醚环、配体芳环上取代基和反应时间等对对二甲苯催化氧化反应的影响。实验结果表明:Schiff碱配合物中氮杂冠醚的存在能显著缩短反应诱导期,提高催化反应活性和产物选择性;Schiff碱Mn(III)配合物比Schiff碱Co(II)具有更高的催化反应活性;氮杂冠醚Schiff碱Mn(III)配合物对于二甲苯的催化氧化反应转化率大于60%,对甲苯甲酸产物的选择性均高于70%。     

Polymer supported catalysts for oxidation of phenol and cyclohexene using hydrogen peroxide as oxidant

Polymer supported transition metal complexes of N,N′-bis (o-hydroxy acetophenone) hydrazine (HPHZ) Schiff base were prepared by anchoring its amino derivative Schiff base (AHPHZ) on cross-linked (6 wt%) polymer beads and then loading iron(III), copper(II) and zinc(II) ions in methanol. The loading of HPHZ Schiff base on polymer beads was 3.436 mmol g⁻¹ and efficiency of complexation of polymer anchored HPHZ Schiff base for iron(III), copper(II) and zinc(II) ions was 83.21, 83.40 and 83.17%, respectively. The efficiency of complexation of unsupported HPHZ Schiff base for these metal ions was lower than polymer supported HPHZ Schiff base. The structural information obtained by spectral, magnetic and elemental analysis has suggested octahedral and square planar geometry for iron(III) and copper(II) ions complexes, respectively, with paramagnetic behavior, but zinc(II) ions complexes were tetrahedral in shape with diamagnetic behavior. The complexation with metal ions has increased thermal stability of polymer anchored HPHZ Schiff base. The catalytic activity of unsupported and polymer supported HPHZ Schiff base complexes of metal ions was evaluated by studying the oxidation of phenol (Ph) and epoxidation of cyclohexene (CH). The polymer supported metal complexes showed better catalytic activity than unsupported metal complexes. The catalytic activity of metal complexes was optimum at a molar ratio of 1:1:1 of substrate to oxidant and catalyst. The selectivity for catechol (CTL) and epoxy cyclohexane (ECH) in oxidation of phenol and epoxidation of cyclohexene was better with polymer supported metal complexes in comparison to unsupported metal complexes. The energy of activation for oxidation of phenol (22.8 kJ mol⁻¹) and epoxidation of cyclohexene (8.9 kJ mol⁻¹) was lowest with polymer supported complexes of iron(III) ions than polymer supported Schiff base complexes of copper(II) and zinc(II) ions.     

PREPARATION AND CATALYTIC PROPERTIES OF POLYMER-BOUND SCHIFF BASE TERNARY COMPLEXES

ABSTRACT

The polymer-bound Schiff base ternary cobalt complexes (PS-SalPhe-Co-L (L=Phen, Bipy and 8HQ)) have been prepared from the polymer bound Schiff base ligand, cobalt salt and the second ligand, such as 1,10-phenanthroline(phen), 2,2′-bipyridyl(bipy) and 8-quinolinol(8HQ). The polymer-bound Schiff base ternary cobalt complexes were characterized by the infrared spectra and ICP-AES. The catalytic activity of the complexes has been studied in aerobic epoxidation of long-chain linear aliphatic olefins. It showed that 1-octene or 1-decene can be directly oxidized by molecular oxygen catalyzed by PS-SalPhe-Co-L (L=Phen, Bipy and 8HQ), which afford the 1,2-epoxy alkane.     

手性席夫碱配合物用于催化不对称环氧化

手性席夫碱过渡金属配合物可以高效催化烯烃不对称环氧化反应,因此其合成及催化性能研究一直以来受到广泛的关注.本文较详细地综述了最近十年来合成的手性席夫碱过渡金属配合物及其对烯烃环氧化反应的催化性能的研究进展.重点讨论了新型的对称和非对称salen型配体过渡金属配合物的合成及其应用,分析探讨了手性席夫碱过渡金属配合物作为催化剂的优缺点、催化机理和未来发展方向.     

Schiff碱配合物的研究——Ⅸ.表面Schiff碱配合物对H_2O_2分解的催化作用

制备了两种表面Schiff碱及其Cu~(2+)、Co~(2+)、Ni~(2+)、Zn~(2+)配合物,考察了它们对H_2O_2分解的催化性能,其活性顺序为:Co~(2+)>Cu~(2+)>Ni~(2+)>Zn~(2+),且与金属离子氧化还原电位有关。溶液的pH值增加有利于催化反应,有机配体的加入则对反应有所抑制。     

Chromone-based Schiff base metal complexes as catalysts for catechol oxidation: Synthesis,kinetics and electrochemical studies

Two new Schiff base ligands with chromone moiety and their transition metal complexes were synthesized and characterized by elemental analyses, magnetic susceptibility, molar conductance and TGA analyses, FT IR, UV-Vis, NMR and mass spectroscopy. All the complexes synthesized have been investigated as functional models for catechol oxidase (catecholase) activity by employing 3,5-di-tert-butylcatechol as a model substrate. The two mononuclear copper(II) and two mononuclear iron(II) complexes show catecholase activity with turnover (k_cat) numbers lying in the range 27.2–1328.4 h^?1. According to the kinetic measurement results, the rate of catechol oxidation follows first order kinetics and iron(II) complexes were found to have higher catalytic activity than those of copper(II) complexes. Electron-donating substituent on Schiff base ligand enhanced the catalytic activity of metal complexes while the electron-withdrawing substituent led to a decrease in activity. The electrochemical properties of two Schiff bases and their metal complexes were also investigated by Cyclic Voltammetry (CV) using glassy carbon electrode (GCE) at various scan rates. Electrochemical processes of all the compounds were observed as irreversible.