环钯化二茂铁亚胺-三苯基膦配合物的合成、表征及催化Suzuki反应研究

为筛选高效催化Suzuki反应的催化剂, 合成了3种新的环钯化二茂铁亚胺-三苯基膦配合物2~4, 经元素分析(或HRMS)、 红外光谱和核磁共振谱对其结构进行了表征, 并通过X射线单晶衍射测定了化合物3的晶体结构. 这些化合物容易合成, 在空气和溶液中稳定, 可用作芳基溴及杂芳基溴与苯基硼酸偶联的Suzuki反应催化剂. 使用摩尔分数为0.01%的催化剂3, 以2倍量的K3PO4为碱, 于110 ℃下, 在甲苯中反应5~15 h, 使具有不同电子和位阻效应的取代芳基溴及杂芳基溴能以较高的产率与苯基硼酸反应生成偶联产物; 与溴苯相比, 带吸电子基的溴苯反应活性较高, 催化剂的摩尔分数降低至0.001%时, 仍能得到较高产率, 而带强给电子基的溴苯如4-溴苯甲醚及带邻位取代基的溴苯在其它条件相同时, 需要延长反应时间才能得到较高的产率.     

痕量环钯配合物高效催化合成二茂铁衍生物

选用新型双二茂铁亚胺环钯配合物(Fc2C NPh)Pd Cl PPh3(Fc=Ferrocenyl,Ph=Phenyl)作为催化剂,通过碘代二茂铁作为反应底物,进行Suzuki-Miyaura交叉偶联反应,以良好产率,合成了一系列具有特殊取代基的二茂铁衍生物(1~9).优化了制备二茂铁衍生物的交叉偶联反应条件,考察了底物适应范围,给出了优化合成路线,推测了催化反应机理.结果表明,选用的环钯配合物催化剂对潮气和空气不敏感,具有催化剂用量少(痕量)、催化反应活性高、底物适应范围宽等优点,是制备二茂铁衍生物的理想催化剂.     

含二茂铁基聚合物的合成及应用研究进展

二茂铁基聚合物由于具有独特的结构特点,使其在电化学、催化、材料等方面受到了广泛的关注.二茂铁聚合物的种类较多且合成方法多种多样.本文综述了近年来含二茂铁基聚合物的合成及应用.从缩聚、开环聚合和接枝共聚等方面介绍了近年来二茂铁基聚合物的合成方法,讨论了二茂铁基聚合物在电化学、生物材料及其他方面的应用.最后,对二茂铁基聚合...     

双（甲基二茂铁基）代烷羟的合成

二茂铁衍生物在复合固体火箭推进剂中用作燃速催化剂,但其挥发性和迁移性较大,直接影响储存或使用时导弹的弹导性能。本文报导三种新型燃速催化剂:双(甲基二茂铁基)甲烷,2,2-双(甲基二茂铁基)丙烷和2,2-双(甲基二茂铁基)丁烷的合成和表征。小型试验表明其催化活性、挥发性及迁移性能均优于国内目前使用的叔丁基二茂铁。     

多二茂铁基二氮杂己烷及其过渡金属配合物的合成

乙二胺与二茂铁甲醛或双二茂铁甲基氟硼酸盐反应，合成了１，６－二（二茂铁基）－２，５－二氮杂己烷和１，１，６，６－四（二茂铁基）－２，５－二氮己烷，它们与过渡金属（Ｆｅ＾２＋，Ｃｏ＾２＋，Ｎｉ＾２＋，Ｃｕ＾２＋，Ｚｎ＾２＋）盐在乙醇或乙醇－二氯甲烷中反应，是１４种过渡金属配合物，对这些化合物进行了表征，二种配体及其铜配合物用作复合固体推进剂的燃速调节剂时，基本不迁移，而燃速催化效率均超过辛基二茂铁。     

二茂铁基1,4-Dihydropyridine类似物的合成

1 ,4 二氢吡啶衍生物是一类有着多种生物活性的化合物 ,具有扩张血管、抗高血压、抗动脉粥状硬化、抗肿瘤、抗糖尿病、抗衰老等作用 ,是七十年代以来相继开发的一类新型高效的钙离子拮抗剂 ,临床上用于治疗高血压、心绞痛、充血性心衰和动脉粥状硬化等心脑血管疾病及肠胃疾病、雷诺氏病 ,还可以作为辅佐药物治疗肺动脉高压和癫痫病[1 ] 。近年来 ,二茂铁衍生物在生物学、医学等方面得到了广泛的研究和应用 ,主要是由于它们的结构和性质有自身的特殊性 :二茂铁有卓越的芳香性 ,易发生取代反应 ,易进行修饰 ,并且在许多介质中有较好的稳定性 ;…     

含有酯基二茂铁亚胺环钯化合物催化Suzuki和Heck反应

合成并表征了系列含有酯基二茂铁亚胺环钯化合物.结果表明,该系列环钯催化剂在纯水或有机溶剂中均能高效催化Heck和Suzuki偶联反应.     

Dioxomolybdenum(VI) complexes of hydrazone phenolate ligands - syntheses and activities in catalytic oxidation reactions

The new cis-dioxomolybdenum (VI) complexes [MoO₂(L²)(H₂O)] (2) and [MoO₂(L³)(H₂O)] (3) containing the tridentate hydrazone-based ligands (H₂L² = N'-(3,5-di-tert-butyl-2-hydroxybenzylidene)-4-methylbenzohydrazide and H₂L³ = N'-(2-hydroxybenzylidene)-2-(hydroxyimino)propanehydrazide) have been synthesized and characterized via IR, ¹H and ¹³C NMR spectroscopy, mass spectrometry, and single crystal X-ray diffraction analysis. The catalytic activities of complexes 2 and 3, and the analogous known complex [MoO₂(L¹)(H₂O)] (1) (H₂L¹ = N'-(2-hydroxybenzylidene)-4-methylbenzohydrazide) have been evaluated for various oxidation reactions, viz. oxygen atom transfer from dimethyl sulfoxide to triphenylphosphine, sulfoxidation of methyl-p-tolylsulfide or epoxidation of different alkenes using tert-butyl hydroperoxide as terminal oxidant. The catalytic activities were found to be comparable for all three complexes, but complexes 1 and 3 showed better catalytic performances than complex 2, which contains a more sterically demanding ligand than the other two complexes.     

Synthesis,characterization and pronounced epoxidation activity of cis-dioxo-molybdenum(VI) tridentate Schiff base complexes using tert-butyl hydroperoxide

The synthesis and catalytic performance of novel cis-dioxo-Mo(VI) complexes containing simple ONO tridentate Schiff base ligands in the epoxidation of various olefins using tert-butyl hydroperoxide in desired times with excellent chemo- and stereoselectivity have been described. The study of turnover numbers and the UV–Vis spectra of the Mo complexes in the present epoxidation system indicate well the high efficiency and stability of the catalysts during the reaction. The electron-deficient and bulky groups on the salicylidene ring of the ligand promote the effectiveness of the catalyst.     

Dioxomolybdenum(VI) complexes of hydrazones of two substituted salicylaldehydes: synthesis,structures, and catalytic properties

Dioxomolybdenum(VI) complexes [MoO₂L(CH₃OH)] (L?=?L¹?=?N′-(2-hydroxy-5nitrobenzylidene)isonicotinoylhydrazide for 1, L?=?L²?=?N′-(4-diethylamino-2-hydroxybenzylidene)-4-methylbenzohydrazide for 2) were prepared and structurally characterized by physicochemical and spectroscopic methods and single-crystal X-ray determination. Mo in the complexes is octahedrally coordinated. Both complexes show effective catalysis in oxidation of cyclohexene, vinylbenzene, 1-butylene, and 1-pentene, to their corresponding epoxides. In general, high epoxide yields (over 89%) and selectivity (100%) were observed for all aliphatic and aromatic substrates.     

Characterization of a Novel Dioxomolybdenum Complex by Cyclic Voltammetry

Metalloenzymes that carry a pterin-based molybdenum cofactor in their center catalyze numerous reactions in the human body and play a crucial role in its metabolism. Specifically, these enzymes promote redox reactions and oxygen transport in the body. Their absence may cause many problems leading to disability or even death in early childhood. Therefore, model compounds need to be synthesized and analyzed to investigate the reactivity, redox potential, and geometry of these cofactors. This study focused on electrode processes and determined the redox potentials of the new bis-(4-mercapto-5-(p-tolyl)-3H-1,2-dithiole-3-thione)-dioxomolybdenum complex by cyclic voltammetry. The 4-mercapto-5-(p-tolyl)-3H-1,2-dithiole-3-thione ligand underwent irreversible oxidation and reduction at thiol and thione functional groups. The new dioxomolybdenum complex showed a quasi-reversible two-stage electrode process.     

Ligandenaustauschreaktionen von Bis(acetylacetonato)dioxo-molybdän(VI). Kristallstrukturen von [Salicylaldehyd-benzoylhydrazonato(2–)]dioxo-methanol-molybdän(VI) und [Benzoylaceton-benzoylhydrazonato(2–)] dioxo-triphenylphosphanoxid-molybdän(VI)

Ligand Exchange Reactions of Bis(acetylacetonato)dioxo-molybdenum(VI). Crystal Structures of [Salicylaldehyde-benzoylhydrazonato(2–)]dioxo-methanol-molybdenum(VI) and [Benzoylacetone-benzoylhydrazonato(2–)]dioxo-triphenylphosphaneoxide-molybdenum(VI) The products of ligand exchange reactions between bis(acetylacetonato)dioxo-molybdenum(VI) and tridentate diacidic ligands H₂L in the presence of triphenylphosphane were found by mass spectrometry to be complexes of the type MoO₂L. In the case of salicylaldehyde 2-hydroxyanil MoL₂ could also be identified. The compounds MoO₂L were crystallized as complexes with methanol or triphenylphosphane oxide. Crystallographic data see “Inhaltsübersicht”.     

Synthesis and Crystal Structure of a Dioxomolybdenum(VI) Complex Derived from 2-Bromo-N'-(3,5-dichloro-2-hydroxybenzylidene)benzohydrazide with Catalytic Epoxidation Property

Russian Journal of Coordination Chemistry - A dioxomolybdenum(VI) complex [MoO2L(EtOH)] (I), derived from the hydrazone ligand 2?bromo-N'-(3,5-dichloro-2-hydroxybenzylidene)benzohydrazide...     

Effects of the preparation method and calcination temperature on Cu–Cr–Mg–Al catalysts for the dehydrogenation of cyclohexanol

Novel dioxomolybdenum(VI) complexes bearing bis(ferrocenylcarbaldimine) ligands were prepared in good yield and characterized by spectroscopy and elemental analysis. The complexes were found to be excellent catalysts for the homogeneous epoxidation of cyclohexene and styrene using tert-butyl hydroperoxide (TBHP) as oxidant. The complexes can be recovered and reused.     

Dioxomolybdenum(VI) Complex with (1-Oxyethylidene)diphosphonic Acid in an Aqueous Medium: Synthesis and Crystal Structure

Russian Journal of Coordination Chemistry - A new complex of hexaammonium bis(1-oxyethylidenediphosphonate)dioxomolybdenum tetrahydrate (NH4)6[MoO2(L)2] · 4H2O (I) (H4L is...     

乙二醛缩双(邻氨基苯酚)合锰(II)配合物的合成及其催化行为研究

合成了乙二醛缩双(邻氨基苯酚)合锰(II)配合物, 讨论了其在DMF中的载氧行为、氧合动力学; 设计正交试验考察了以分子氧为氧源, 该配合物催化氧化醋酸去氢表雄酮生成7-酮基醋酸去氢表雄酮的性能, 最高收率达78.4%.