CO在载钯分子筛薄膜电极上的增强红外吸收

以NaY分子筛超笼为微型反应器,通过“瓶中造船”技术合成钯原子簇(Pd₁₃).并首次把粗糙的分子筛薄膜电极引入到电化学原位红外反射光谱研究,发现了一类新的增强红外吸收现象.与金属钯电极相比,CO红外吸收带的谱峰强度显著增加,半峰宽加宽.研究结果表明,这种增强红外吸收取决于钯原子簇的纳米尺度及分子筛超笼的特殊环境.     

含氢碳原子团簇的初步研究

介绍直接用激光溅射芳香化合物固态样品产生的含氢磷原子团簇离子（C_nH~＋_m），并用飞行时间质谱仪研究了其组成和结构．实验发现，在低质量区（n＝32－56）得到了具有奇偶碳原子数的含氢磷原子簇，而在高质量区（n＞100）除了得到纯碳原子簇以外，还得到了含氢碳原子簇．根据对实验结果的分析提出了两种结构模型：对低质量区的团簇，其结构为芳香基团与富勒烯笼状框架的复合体；对高质量区的团簇，其结构为蜗牛形与圆柱形的复合体．     

笼形聚偕胺肟树脂的研究──Pd(Ⅱ)在碱式树脂上的吸附动力学

研究了碱式笼形聚偕胺树脂（BCAO）吸附Pd（Ⅱ）的行为．溶液pH值对吸附容量有重要的影响．在一定条件下,BCAO在中性溶液中吸附Pd（Ⅱ）的量是酸性溶液中的一倍以上,但提高溶液的酸性有利于从稀溶液中回收钯．Pd（Ⅱ）在盐酸溶液中显H_2PdCI_4结构．吸附结果生成AO－Pd络合物．当溶液被碱中和至近中性时,Pd（Ⅱ）以Pd~(2+)和[Pd（OH）_2CI_2]2-的形式存在,吸附过程中先后生成AO－Pd,AO-Pd_2和AO_2－Pd_3先等不同组成的给合物．由于AO与Pd（Ⅲ）之间较大的电位差,部分Pd（Ⅱ）被还原成Pd（0）,并汇聚在BCAO表面上．     

Mo（W）－Cu（Ag）－S原子簇化合物的研究现状

本文在研究Ｍｏ（Ｗ）－Ｃｕ（Ａｇ）－Ｓ原子簇化合物的低热固态合成化学基础上，详细地对该类簇合物进行了归纳，从中提出：１．（Ｍ＝Ｍｏ，Ｗ；ｎ＝２，３，４）作为配体中心．２．氧原子在簇合物中仅作为端基，不参与同其他金属成键．３．单个ＭＳ４（Ｍ＝Ｍｏ，Ｗ）基团最多只能键合六个Ｃｕ（Ａｇ）原子，即最大核数为七．４．迄今为止所有Ｍｏ（Ｗ）－Ｃｕ－Ｓ原子簇化合物中Ｃｕ均为＋１价．５．预计合低价态Ｍｏ（Ｗ）的这类簇合物将会有很大进展．     

［Ru_6（CO）_（18）］~（2－）在NaX分子筛超笼中的合成和表征

在ＮａＸ分子筛超笼中通过ＲｕⅢ（ＮＨ３）６同ＣＯ＋Ｈ２反应合成了［Ｒｕ６（ＣＯ）１８］２－原子簇阴离子．原子簇阴离子上的羰基配体在氢气存在时具有一定的１３ＣＯ同位素交换活性．ＥＸＡＦＳ的数据表明，８０─９０％的钌原子在ＮａＸ分子筛中以［Ｒｕ６（ＣＯ）１８］２－的方式存在．分子筛笼中的原子簇阴离子在氧化气氛下解离成单核钌羰基物种Ｒｕ１（ＣＯ）２，两者的结构在氧化（Ｏ２）及还原（ＣＯ＋Ｈ２）条件下可以进行可逆转化．     

利用SHIP－IN－BOTTLE技术在NaY分子筛中合成Ru_8（CO）_（12）原子簇

利用ＳＨＩＰ－ＩＮ－ＢＯＴＴＬＥ技术在ＮａＹ分子筛中合成Ｒｕ_８（ＣＯ）_（１２）原子簇肖丰收，徐如人，何亚男，丁红，张艳秋（吉林大学化学系，长春，１３００２３）关键词原子簇，Ｒｕ_３（ＣＯ）_１２，ＮａＹ分子筛，钌，羰基在多相催化研究中，金属羰基簇合物...     

Pd(Hmp)2(PBn3)2的合成、晶体结构及其二聚机理

膦巯混合配位钯化合物Pd（Hmp）_2（（PBu_3~n）_2）（1）含有四方平面构型的二价钯，PdS和Pd-P的键长分别为2．338（1）和2．336（1），在过量的邻巯基苯酚存在下生成．如果是膦过量，则生成以核配合物Pd_2（Hmp）（PBu_3~n）_2Cl_2[1]．文中讨论了（1）和（2）的生成机理和Pd（Hmp）_2（PM_（e3））_2的量化计算结果．     

铜配合物在Y型分子筛超笼中的组装及其催化苯酚羟化活性

 详尽介绍了通过分步法，在Y型分子筛超笼中制备铜（II）- 1，10菲咯啉和8-羟基喹啉配合物（简称CuPhen/Y，CuOx/Y）的过程；活性评价结果显示同Cu/Y相比，以H2O2为氧化剂，CuPhen/Y，CuOx/Y具有特殊的催化苯酚羟化功能。     

Ru3(CO)(12)在NaY分子筛超笼中的结构表征

采用单层分散法将Ｒｕ３（ＣＯ）１２引入ＮａＹ分子筛的孔道中，借助ＦＴＩＲ，ＥＸＡＦＳ和ＵＶ－ＶＩＳ等实验手段对其进行了测定，发现Ｒｕ３（ＣＯ）１２完整地分布于分子筛的超笼内，抽空会导致在保持金属骨架情况下的部分脱羰，同时伴随着桥式羰基谱带的出现，这意味表面次羰基合物的形成，原子簇上的羰，同时伴随着桥式羰基谱带的出现，这意味着表面次羰基加合物的形成，原子簇上的羰基配体可以同１３ＣＯ同位素进行交换反应     

Mo（W）－Co（Ni，Fe）簇合物的加氢脱硫催化活性

对线型、立方烷型和笼状３种不同构型的Ｍｏ（Ｗ）－Ｃｏ（Ｎｉ，Ｆｅ）－Ｓ（Ｏ）簇共１２种化合物进行了噻吩加氢脱硫和环己烯加氢的催化活性研究．讨论了簇合物的组成，金属原子的配比、价态与催化活性的关系．探讨了不同构型对活性的影响．     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.