卟啉化合物的研究——ⅩⅤ.双卟啉的合成及其与钴离子的络合反应

将双卟啉化合物作为“合成反应中心”是人工光合作用研究中很活跃的一个领域。困难的是,人们还不知道怎样排布两个卟啉环,分子才具有最有效传递电子和能量的构象。本文按下列反应合成了一个以柔性链连接的双卟啉化合物(3),以期当分子中络合金属后,籍助两个金属的协同作用和链的可塑性,达到在光反应过程中取最佳构象的目的(见图1)。化合物(1)按文献[1]合成。2、3尚未见报道,它们的结构,经元素分析及波谱分析确认。本文还研究了3与Co~(2 )络合反应的动力     

尼龙1216晶型转变的红外光谱研究

采用变温红外光谱研究了尼龙1216的Brill转变并测得Brill温度约为150℃。一些α谱带在转变过程中消失，氢键强度也急剧减弱。这些现象证明了Brill转变的“局部熔融”机理。     

2,6-二(对氨基苯)苯并[1,2-d;5,4-d′]二噁唑的合成和纯化

1 ,2 ,3 三氯苯经过硝化、水解、催化加氢、缩合等四步反应 ,合成了 2 ,6 二 (对氨基苯 )苯并 [1,2 d ;5 ,4 d′]二唑 ,总产率为 70 % .同时 ,研究了一种有效的重结晶 2 ,6 二 (对氨基苯 )苯并 [1,2 d ;5 ,4 d′]二唑的方法 .与其他方法相比 ,该法原料便宜易得 ,产物可作为聚合反应的单体原料 .     

2,2’-联吡啶-1,1’-二氧化物与Mn(Ⅱ)的三聚体配合物的合成及性能

Mn( )能与许多氮氧化合物形成配合物 ,Wilde对 Mn( )与 2 ,2 -联吡啶及 1 ,1 -二氮杂菲的均配配合物作过详细研究 [1,2 ] ;Mn( )与 2 ,2 -联吡啶 - 1 ,1 -二氧化物 ( bipy O2 )的配合物也有综述 [3] .Mn( )与 bipy O2 的配合物大多是以 Cl O- 4、NO- 3、[Pt Cl4 ]2 -为阴离子 ,少数是卤离子 .它们均形成配位体数目为 3的单核螯合物 ,这些配合物是在水或乙醇中合成的 .Mn( )与 bipy O2 的多核聚合物还未见报道 .本文用 DMF为溶剂 ,以无水 Mn Cl2 和 2 ,2 -联吡啶 - 1 ,1 -二氧化物为原料 ,合成了 Mn( )与bipy O2 的三聚…     

水热法制备高纯超细CeO2-ZrO2复合氧化物

Superfine composite powders of CeO₂-ZrO₂ (CZ) and CeO₂-ZrO₂-La₂O₃ (CZL) were prepared by hydrothermal method. The effects of pH、temperature and time for hydrothermal process on the performance of the resulting powders were studied. The optimized reaction parameters were on follows: the precursor′s pH≈9.0, hydrothermal temperature of 200 ℃ holding for 2 h. Thermal stable powders with average particle size smaller than 10 nm and specific surface area of 171 m²·g^-1 were obtained. A BET specific surface area was still at 44 m²·g^-1 after calcination at 1 000 ℃ for 6 hours.     

二苯并18－冠－6辅助钡离子在1，2－二氯乙烷／水微界面转移的伏安研究

应用液／液界面微电极对二苯并１８－冠－６（ＤＢ１８－Ｃ－６）辅助推动Ｂａ~（２＋）在１，２－二氯乙烷／水（ＤＣＥ／Ｗ）界面转移的电化学过程进行了详细探讨，证明该过程遵循ＴＩＣ机理，是受扩散控制的可逆过程。通过转移电流和反应物浓度之间的线性关系，测定了Ｂａ~（２＋）以及用其它方法难以测定的ＤＢ１８－Ｃ－６。     

Reaction Ergodography and Transition State Analyses of the Addition of AIH_3 to Acetylene

The present paper covers the reaction ergodography for the addition of AlH3 to acetylene investigated by ab initio calculation with RHF/3-21G basis set. The changes in some physical properties along the reaction path (IRC) are presented. The formations of FMOs of the transition state have been analyzed according to the Fukui' s method. On the basis of the perturbation theory and Wolfsborg Helmholtz formula, we calculated the FMO' s energy orders of TS and its formation that shows the HOMO of TS consists of LUMO, HOMO of AlH3 and HOMO of HCCH.     

Crystal Structure of (3S, 6S, 7R, 8R)-3,6-Bis-diphenylphosphino-1,4-dioxabicyclo〔3.3.0〕octane

1INTRoDUCTIONThetitlecompoundhasbeenfoundtobeaveryefficientchiralligandusedtoco-ordinatewithpalladiumformingcatalystsystemsforasymmetrichydroesterificationofnorborneneandstyrene.Intheseasymmetriccatalyticreactions,thechiralinduc-tionofthetitlecompoundisratherstronggivingveryhighoptica1yields(>9o%)ofproductstl3.Inordertostudytherelationshipoftheperformanceandthestructureofthisligand,itisimportanttodeterminethemolecularstructureofthechiraldiphos-phinecompound,whichwaspreparedbytheliteraturem…     

An Efficient Deselenenylation Reaction to the Synthesis of 3, 5-Disubstituted Isoxazoline and Isoxazole

The development of organoselenium chemistry1 has been expanding rapidly during the last decades. Among them, organic selenides are key intermediates, for that they can be efficiently introduced, manipulated, and removed through selenoxide syn-elimination2. Our research group3 has been interested in the application of selenium in organic synthesis for several years. Isoxazolinyl substituted phenyl selenide 13a, although a β-H exists in the molecule, did not undergo selenoxide syn-elimination e…     

Synthesis and Crystal Structure of Binuclear Copper （Ⅱ） Complex Containing （Dimethylaminomethyl）ferrocene

1 INTRODUCTION Transition metal complexes with ferrocene are of considerable interest in the past fifty years because of their novel structures and special properties[1, 2]. The chemistry of ferrocene and its derivatives has become richer and richer in the last decade. Many complexes containing ferrocenyl have been synthesized and characterized[3～5]. Recently we have reported the synthesis and crystal structure of dibromo[1,1?bis(diphenylphosphino)- ferrocene]cadmium (Ⅱ)[6]. Herein we…