2,2′-联咪唑衍生物铜配合物的合成、表征及光谱性质

本文合成了1,1′-二（丙酸甲酯）-2,2′-联咪唑和1,1′-二（丙酸乙酯）-2,2′-联咪唑两个配体,并以无水乙醇为溶剂,在常温条件下合成了配体与铜的配合物。通过IR、UV、EA表征,推测其形成了1：1的配合物。铜配位后使两种配体发生荧光猝灭。     

微波辅助合成5-[4-(4-溴代丁氧基)苯基]-10,15,20-三对甲氧基苯基卟啉

探讨采用微波辅助合成尾式卟啉（p-BrTMOPP）的制备工艺及其影响因素。以吡咯、对羟基苯甲醛和对甲氧基苯甲醛为原料,以丙酸为溶剂,制备得到p-HTMOPP;以1,4-二溴丁烷为原料,微波辅助加热条件下制备得到目标化合物尾式卟啉p-BrTMOPP;目标产物经过UV-vis、IR、ESI-MS等方法表征。在90℃、DMF溶剂条件下微波辐射加热30min,快速高效得到目标化合物,反应产率89.2%。和传统加热方法相比较,微波辅助合成尾式卟啉化合物明显缩短了反应时间,提高了反应效率。     

钴卟啉轴向配位反应的紫外可见及圆二色谱研究

用紫外-可见光谱和圆二色谱研究了氯乙酸胆甾酯钴卟啉和桥联冠醚钴卟啉在CHCl3中的光谱行为,探讨了氯乙酸胆甾酯钴卟啉和桥联冠醚钴卟啉与咪唑、苯骈咪唑轴向配位前后的光谱变化。实验结果表明:在反应体系中不同的配体具有不同的最佳浓度:氯乙酸胆甾酯钴卟啉体系中,咪唑、苯骈咪唑的最佳浓度分别为7.5×10-4mol/L,2.5×10-4mol/L,低于最佳浓度时有利于增强CD光谱的强度和对称性,高于最佳浓度则减弱了CD光谱的强度并且使峰形变复杂;同时卟啉和咪唑类分子的结构均对反应体系的紫外-可见光谱和圆二色光谱的峰形、强度和波长产生影响。     

N-甲基咪唑膦/钯催化Sonogashira偶联反应研究

系统考察了三种N-甲基咪唑膦配体在钯催化的Sonogashira反应中的催化活性。结果表明,这三种咪唑膦配体配体与氯化钯形成的络合物均能有效地催化溴苯与苯乙炔的Sonogashira偶联反应,催化活性随着咪唑环的个数增多呈现下降的趋势,其中单咪唑化合物L1催化活性最高。通过优化反应条件,在100℃条件下,以乙醇为溶剂,六氢吡啶为碱,单咪唑膦化合物L1/氯化钯体系能够有效催化不同溴代芳烃与苯乙炔的Sonogashira偶联反应。     

Enantioselective epoxidation catalyzed by silicagel supported (Salen)-Mn (Ⅲ) complex in ionic liquid

进行了以Jacobsen催化剂、硅胶型 (Salen)-Mn（Ⅲ）配合物为催化剂（1,2）,以离子液体1-丁基-3-甲基咪唑四氟硼酸盐（BMIMBF₄）和1-丁基-3-甲基咪唑六氟磷酸盐（BMIMPF₆）为反应介质,次氯酸钠为氧化剂,乙酸铵为轴向配体催化非官能团烯烃（苯乙烯、α-甲基苯乙烯、茚）的不对称环氧化反应。通过实验对比发现,反应介质离子液体与二氯甲烷相比可以有效提高催化反应的速率和ee值,并且离子液体BMIMPF₆辅助催化能力高于（BMIMBF₄）;硅胶载体型配合物在离子液中催化烯烃具有比均相Jacobsen催化剂更好的立体催化效果。如a-甲基苯乙烯,在离子液BMIMPF₆反应中获到97%～100%的ee值,且反应循环5次后催化剂活性没有明显的下降。     

不对称酰胺基液晶化合物的合成,表征及热分析

以CH2Cl2为溶剂,通过5-（4-氨基）苯基-10,15,20-三苯基卟啉（MATPP）与硬脂酸直接反应得到一种新型不对称酰胺基卟啉配体5-（4-硬脂酸酰亚胺基）苯基-10,15,20-三苯基卟啉配体（SITPPH2）,利用紫外-可见光谱、红外光谱、核磁共振氢谱、质谱、元素分析等测试方法对化合物的结构加以确认。热分析表明,卟啉配体从200℃开始分解,具有较高的热稳定性。     

四苯基卟啉和金属卟啉的制备

采用二甲苯为溶剂,对硝基苯甲酸催化,苯甲醛和吡咯反应合成四苯基卟啉（ＴＰＰ）,产率可达５５４％;另外,用ＤＭＦ为溶剂,ＴＰＰ与醋酸锌反应生成金属卟啉锌（ＴＰＰＺｎ）,产率可达９７６％。     

甲苯基卟啉和金属卟啉的制备

采用二甲苯为溶剂，对硝基苯甲酸催化，苯甲醛和吡咯反应合成四苯基卟啉（ＴＰＰ），产率可灰５５．４％；另外，用ＤＭＦ为溶剂，ＴＰＰ与醋酸锌反应生成金属卟啉锌（ＴＰＰＺｎ），产率可达９７．６％。     

离子液体辅助硅胶型(Salen)-Mn(Ⅲ)催化烯烃不对称环氧化

进行了以Jacobsen催化剂、硅胶型(Salen)-Mn(Ⅲ)配合物为催化剂(1,2),以离子液体1-丁基-3-甲基咪唑四氟硼酸盐(BMIMBF4)和1-丁基-3-甲基咪唑六氟磷酸盐(BMIMPF6)为反应介质,次氯酸钠为氧化剂,乙酸铵为轴向配体催化非官能团烯烃(苯乙烯、α-甲基笨乙烯、茚)的不对称环氧化反应.通过实...     

微囊型铁卟啉的制备及催化氧化环己烷研究

将四苯基铁(Ⅲ)卟啉包埋在苯乙烯和二乙烯苯的共聚物中制备微囊型催化剂。研究了苯乙烯和二乙烯苯摩尔比和搅拌速度对微囊型催化剂制备的影响,结果表明,苯乙烯和二乙烯苯摩尔比为1∶1,搅拌速度为800r/m in时,催化剂的粒子表面光滑、圆整。通过红外、扫描电镜对其进行了表征。用所制备的微囊型催化剂催化环己烷氧化,比游离的铁卟啉催化活性高,当其粒径在30~50μm时,环己醇产率为73.5%。该催化剂回收使用5次后,环己醇的产率仍可达到63.1%。     

Salen锰催化不对称环氧化烯烃及固载的研究现状

Salen-Mn(Ⅲ)配合物与卟啉铁的结构和性质相似,其在不对称催化反应中具有高对映异构选择性。重点介绍了Salen-Mn(Ⅲ)的配体合成方法、其催化环氧化反应的机理,并对影响催化不对称环氧化反应因素进行了详细阐述。将Salen-Mn(Ⅲ)固载到固体载体上,催化剂分子充分分离,避免形成片μ-oxo-Mn(Ⅵ)二聚体,从而保持催化剂的活性,并易于回收均相催化剂固载化技术的应用,有力地推动了金属Salen-Mn(Ⅲ)配合物应用研究的发展。     

Selective molecular oxygen transport through a cellulose acetate membrane containing an electron-poor iron(II) porphyrin complexes

Molecular oxygen diffusion in the cellulose acetate membranes containing the 5,10,15, 20-tetrakis(pentafluorophenyl)-21H,23H-porphine iron(II) was studied. Both the permeability coefficient and the separation factor for oxygen in the membrane containing the iron(II) porphyrin complex were increased with decreasing the upstream gas pressure which correspond to a dual-mode oxygen transport. The effects of the axial ligands of the iron(II) porphyrin on oxygen permeation was also examined in the same cellulose acetate membrane. The fluoride and 2-methyl imidazole ligands coordination to the iron(II) porphyrin induce to increase the oxygen permeability coefficient and the value of ideal separation factor.     

Peculiar sandwich-like π–π interaction regulating the nonplanarity of the model heme crystals

X-ray crystallographic analysis of bis(pyridine N-oxide) complexes of iron(III) porphyrinates has revealed that the two pyridine rings of the axial ligands correctly sandwich the porphyrin ring to induce the deformation of commonly observed S₄ saddled porphyrin ring.     

Characterization of Several Metalloporphyrins in Unusual Oxidation States. The Effect of Axial and Equatorial Ligands

The effect of axial and equatorial ligands on the generation of unusual oxidation states in metalloporphyrins is discussed. Selected examples have been taken from the literature. These include the generation of Ni(III) and Ru(III) porphyrins from Ni(II) and Ru(II) complexes containing specific axial and equatorial ligands as well as the generatoin of a Cu(I) metalloporphyrin dianion which is produced upon the overall three-electron reduction of Cu(II) tetracyanoporphyrin. Special emphasis is placed on the oxidation and reduction of σ bonded iron phenyl porphyrins. These complexes, which are stable as Fe(III), may be oxidized by a single electron to yield unstable compounds characterized as containing a great deal of Fe(IV) character, or reduced by a single electron to produce stable species which resemble, in part, radical anions of Fe(III). This singly deduced species may be described by a resonance equilibria between an Fe(III) porphyrin anion radical and an Fe(II) porphyrin anion. Likewise, the singly oxidized complex may be described by a resonance equilibria between an Fe(IV) porphyrin cation and an Fe(III) cation radical.     

手性麻黄素-卟啉锰催化剂的合成及催化性能的研究

以一类新型的手性麻黄素 -卟啉作配体 ,制备了金属锰配合物。考察了配合物对烯烃环氧化反应的催化性能 ,发现含麻黄素基团的锰卟啉催化剂在烯烃环氧化的两相溶剂 ( CH2 Cl2 /H2 O)体系中 ,不仅催化活性增强 ,同时具有相转移能力。还探讨了反应条件对环氧化结果的影响规律     

Metalloporphyrin/Iodine(III)‐Cocatalyzed Oxygenation of Aromatic Hydrocarbons

Hypervalent iodine species have a pronounced catalytic effect on the metalloporphyrin‐mediated oxygenations of aromatic hydrocarbons. In particular, the oxidation of anthracene to anthraquinone with Oxone readily occurs at room temperature in aqueous acetonitrile in the presence of 5–20 mol% of iodobenzene and 5 mol% of a water‐soluble iron(III)‐porphyrin complex. 2‐tert‐Butylanthracene and phenanthrene also can be oxygenated under similar conditions in the presence of 50 mol% of iodobenzene. The oxidation of styrene in the presence of 20 mol% of iodobenzene leads to a mixture of products of epoxidation and cleavage of the double bond. Partially hydrogenated aromatic hydrocarbons (e.g., 9,10‐dihydroanthracene, 1,2,3,4‐tetrahydronaphthalene, and 2,3‐dihydro‐1H‐indene) afford under these conditions products of oxidation at the benzylic position in moderate yields. The proposed mechanism for these catalytic oxidations includes two catalytic redox cycles: 1) initial oxidation of iodobenzene with Oxone producing the hydroxy(phenyl)iodonium ion and hydrated iodosylbenzene, and 2) the oxidation of iron(III)‐porphyrin to the oxoiron(IV)‐porphyrin cation‐radical complex by the intermediate iodine(III) species. The oxoiron(IV)‐porphyrin cation‐radical complex acts as the actual oxygenating agent toward aromatic hydrocarbons.     

Photokatalytische Aktivierung von molekularem Sauerstoff mittels Eisen(III)porphyrin‐Komplexen

Photochemical charge transfer excitation of tetra‐phenyl(porphyrinato)iron(III) complexes yields tetraphenyl) (porphyrinato)iron(II) which is able to coordinate molecular oxygen under formation of oxo‐[tetraphenyl(porphyrinato)]‐ iron(IV). Based on this photochemical reaction pathway photocatalytic oxygenation of α‐pinene and other alkenes can be initiated. Iron(III) complexes of tetramesitylporphyrin, tetrakis‐(pentafluorophenyl)porphyrin, octa‐β‐bromo‐tetrakis‐(pentafluorophenyl)porphyrin, and octa‐β‐chloro‐tetrakis‐(pentafluorophenyl)porphyrin were investigated photochemically with the aim to improve the low photochemical efficiency of tetraphenyl(porphyrinato)iron(III). The influence of substituents on the porphyrin ligand on the photochemical behavior of the corresponding iron(III) complexes is measured mainly by means of temperature dependent UV/Vis spectroscopy. Both, the yield of oxygenation products formed photocatalytically with α‐pinene and the product distribution (allylic alcohols versus epoxide) depend on the design of the porphyrin ligands coordinated with iron(III).     

苯乙烯分子氧环氧化多相催化剂研究进展

针对近年来国内外苯乙烯分子氧环氧化多相催化剂的研究进展进行了综述,主要介绍了钴系、金系、铁系及其他催化体系等催化剂。其中,钴系催化剂活性高,工艺条件温和,绿色环保,但价格昂贵;金系催化剂在低温条件下对苯乙烯分子氧环氧化表现出良好的活性;铁系催化剂活性低,但经济性好。指出负载型钴系、金系催化剂在苯乙烯分子氧环氧化研究中有潜在的应用前景。