Pd（OAc）2／HQ／FePc,Pd（OAc）2／FePc催化烯烃氧化全面酮的研究

考察了在乙腈酸性水溶液中Ｐｄ（ＯＡｃ）２／氢酯（ＨＱ）／酞青铁（ＦｅＰｃ）和Ｐｄ（ＯＡｃ）／ＦｅＰｃ对环已烯、环戊烯、苯乙烯、正癸烯氧化合成相应酮的催化活性，实验结果表明，两类催化体系对环戊烯的酮基化呈现出较高的催化活性，环戊酮收率可达９８％，在其它烯烃的氧化反应中，三元催化体系Ｐｄ（ＯＡｃ）２／ＨＱ／ＦｅＰｃ的催化活性刘于二元的Ｐｄ（ＯＡｃ）２／ＦｅＰｃ。这表明，在Ｗａｃｋｅｒ类催化体系中，电子     

Pd(OAc)_2/HQ/FePc、Pd(OAc)_2/FePc 催化烯烃氧化合成酮的研究

考察了在乙腈酸性水溶液中Ｐｄ（ＯＡｃ）２／氢醌（ＨＱ）／酞青铁（ＦｅＰｃ）和Ｐｄ（ＯＡｃ）２／ＦｅＰｃ对环己烯、环戊烯、苯乙烯、正癸烯氧化合成相应酮的催化活性．实验结果表明，两类催化体系对环戊烯的酮基化均呈现出较高的催化活性，环戊酮收率可达９８％．在其它烯烃的氧化反应中，三元催化体系Ｐｄ（ＯＡｃ）２／ＨＱ／ＦｅＰｃ的催化活性高于二元的Ｐｄ（ＯＡｃ）２／ＦｅＰｃ．这表明，在Ｗａｃｋｅｒ类催化体系中，电子传递体的作用是很重要的．对催化体系中各组分的作用进行了讨论，并给出了可能的催化作用机理．     

钯催化环己烯氧化合成环己酮

考察了由不同金属酞菁（ＭＰｃ，Ｍ＝Ｆｅ，Ｃｏ，Ｃｕ）氯代金属卟啉（ＭＴＰＰＣ．，Ｍ＝Ｆｅ，Ｃｒ，Ｍｎ）和Ｐｄ（ＯＡｃ）２（醋酸钯）／ＨＱ（氢醌）组成的催化体系对环己烯氧化成环己酮的催化活性。表明，在乙腈酸性水溶液中，Ｐｄ（ＯＡｃ）２／ＨＱ／ＦｅＰｃ催化体系对环己烯氧化合成环己酮显示出较高的催化活性，在３０ｍｉｎ内环己酮收率可达８４％，选择性＞９８％，研究了各种因素对体系催化活性的影响。     

Pd（OAc）2／FePc催化环己烯氧化合成环己酮的研究

考察了几种Ｆｅ－大环配合物与Ｐｄ（ＯＡｃ）２组成的双组分催化体系，在乙腈酸性水溶液中环己烯经合成环己酮的催化活性，实验结果表明，其中以酞菁失（ＦｅＰｃ）与Ｐｄ（ＯＡｃ）２组成的催化体系活性最高，而ＦｅＴＰＰＣｌ与Ｐｄ（ＯＡｃ）２催化体系，虽然催化活性较高，但催化剂的稳定性较低，各种因素对Ｐｄ（ＯＡｃ）２／ＦｅＰｃ催化活催化影响的研究结果指出，在无水和酸存在的非水溶液中，Ｐｄ（ＯＡｃ）２／ＦｅＰｃ对     

Pt／Al_2O_3，Pd／Al_2O_3催化剂上CO氧化与表面氧脱出－恢复性能

Ｐｔ／Ａｌ_２Ｏ_３，Ｐｄ／Ａｌ_２Ｏ_３催化剂上ＣＯ氧化与表面氧脱出－恢复性能周仁贤，郑小明（杭州大学催化研究所，杭州３１００２８）关键词铂，钯，氧化铝，氧化锆，负载型催化剂，一氧化碳，氧化，氧脱附ＡＩ。Ｏ。负载的贵金属（Ｐｔ，Ｐｄ或Ｒｈ等）催化剂对有...     

[Co（p—Me—PPA）2（H2O）2]Cl的合成及其催化环己烯氧化反应的研究

环己烯的选择性氧化是一个较难的课题,原冈是环己烯存在两个活性部位易工发生氧化反应：一是烯两基位的氢易被氧化生成环己烯醇和环己烯酮的产物：二是双键易被氧化成环氧化物、环己酮或Ｃ—ＣＸＸ键断裂生成难成酸等。因此人们一直在努力寻找具有高活性,高选择性的催化剂用以催化环己烯的氧化反应［’＊’］。本文合成的Ｋ叶卜＊卜呷Ａ从比０）。厂１,在０。作氧源下ｍ于催化环己烯氧化反应时呈现出较好的转化率和环己烯酮选择性。１【Ｃｏ（Ｐ－Ｍｅ－ＰＰＡ）。（Ｈ。０）。」Ｃ！的合成采ｍ２一毗咙甲酸和ｐ一甲基本胺作原料合成了【…     

双重负载钯催化剂用于硝基化合物的催化加氢

将可溶的聚乙烯吡咯烷酮负载的钯催化剂进一步负载到γ－Ａｌ２Ｏ３上，得到双重负载的钯催化剂。在少量碱的存在下，这种双重负载的钯催化剂在常温常压下对硝基苯的催化加氢表现出非常高的活性。γ－Ａｌ２Ｏ３负载的聚乙烯吡咯烷酮钯催化剂［ＰＶＰ－Ｐｄ／Ａｌ２Ｏ３（ｍｅｔｈｏｄＢ）］对硝基苯和ｐ－甲基硝基苯加氢的ＴＯＦｍａｘ（ｍａｘｉｍｕｍｔｕｒｎｏｖｅｒｆｒｅｑｕｅｎｃｙ，ｎ（Ｈ２）／（ｎ（Ｐｄ）．ｔ）），分别     

铁助剂对Pd／Al2O3催化剂抗硫性能的影响

借助ＣＯ探针分子原位红外（ｉｎ－ｓｉｔｕＩＲ）、ＴＥＭ（ＥＤＳ）、ＸＰＳ和ＸＲＤ对一系列Ｐｄ－Ｆｅ／Ａｌ_２Ｏ_３、Ｐｄ－Ｐｔ／Ａｌ_２Ｏ_３和Ｐｄ（或Ｐｔ）／Ａｌ_２Ｏ_３模型催化剂进行了表征，结果表明，硫在中毒Ｐｄ（或Ｐｔ）／Ａｌ_２Ｏ_３时，毒物Ｈ_２Ｓ优先吸附于催化剂的多位活性中心上，主要以电子效应影响催化剂的活性．铁的引入，提高了活性组分Ｐｄ的分散度，多位活性中心的减少不利于Ｈ_２Ｓ在催化剂上的吸附；Ｐｄ－Ｆｅ协同作用的结果，增强了催化剂对吸附Ｓ~（２－）氧化成毒性较小的Ｓ~（６＋）或可逸出系统的ＳＯ_２的能力，从而明显地提高了催化剂的抗硫中毒能力．     

CO在Pd／ZrO2—Al2O3催化剂上表面反应性能的研究

用流动反应法和ＴＰＳＲＭＳ等技术研究了ＣＯ在Ｐｄ／γＡｌ２Ｏ３和含有ＺｒＯ２的催化剂上的吸脱附行为、表面反应及催化氧化活性，同时用ＸＲＤ技术测定了催化剂的物相结构。结果表明，在Ｐｄ／γＡｌ２Ｏ３催化剂中用浸渍法添加ＺｒＯ２或掺杂超细ＺｒＯ２后，催化剂的氧化活性均有明显提高；ＣＯＴＰＳＲ的实验结果表明，ＣＯ在氧化态Ｐｄ催化剂上程序升温脱附过程中主要与表面氧发生氧化反应，而在还原态Ｐｄ催化剂上发生歧化反应，并发现ＣＯ２的脱附量及脱附峰温次序与对ＣＯ的氧化活性有一致的对应关系。     

钯盐中负离子对聚合物载钯催化剂加氢性能的影响

将三种钯盐（Ｐｄ（ＯＡｃ）２，ＰｄＣｌ２，ＰｄＩ２）分别与聚乙烯苄二甲胺反应，然后将其还原制成三种不同的高分子负载钯金属催化剂，考察了起始钯盐中负离子的不同对所合成的高分子催化剂表面上钯粒子大小，钯粒子分布状况的影响及催化剂的催化性能。研究结果表明，由Ｐｄ（ＯＡｃ）２制备的高分子载钯催化剂具有最好的催化活性和使用寿命。     

Catalytic oxidation of cyclohexene to cyclohexanone by a triple system in acidic aqueous acetonitrile medium

The catalytic oxidation of cyclohexene to cyclohexanone using Pd(OAc)2/HQ/FePc was investigated in an acidic aqueous solution of acetonitrile. The role of each component of this system in the oxidation of cyclohexene was explored by means of UV-VIS, IR, XPS spectroscopy and cyclic voltammetry, respectively. Based on the experimental results, the mechanism of the oxidation of cyelohexene catalyzed by Pd(OAc)2/HQ/FePc was elucidated.     

FePc结构对Pd(OAc)2/HQ/FePc催化环己烯氧化活性的影响

在乙腈酸性水溶液中,不同来源酞菁铁(FePc)和Pd(OAc)2/HQ（氢醌）组成的催化体系在环己烯氧化反应中有明显不同的催化活性.通过IR、Mssbauer、XPS、XRD、SEM、BET等技术对酞菁铁的分析表明,由酞菁铁组成的多组份催化体系的催化活性与酞菁铁中的飒 氧酞菁铁含量、酞菁铁结晶度和表面形态有关.     

FePc结构对Pd(OAc)_2/HQ/FePc催化环己烯氧化活性的影响

在乙腈酸性水溶液中 ,不同来源酞菁铁 (FePc)和 Pd(OAc)2/HQ(氢醌)组成的催化体系在环己烯氧化反应中有明显不同的催化活性 .通过 IR、 M ssbauer、 XPS、 XRD、 SEM、 BET等技术对酞菁铁的分析表明 ,由酞菁铁组成的多组份催化体系的催化活性与酞菁铁中的μ 氧酞菁铁含量、酞菁铁结晶度和表面形态有关 .     

钯配合物催化烯烃氧化合成酮类物质的研究进展

本文系统地评述了钯配合物催化烯烃氧化合成酮类物质的研究进展。综述了改进Wacker 类催化剂催化活性的几种方法。总结了烯烃氧化合成酮类物质反应的几种典型催化体系及其作用机理。着重介绍了Pd (Ⅱ) HPA (杂多酸)、Pd (Ⅱ) FePc (酞菁铁)、Pd (Ⅱ) HQ (氢醌) FePc、Pd (Ⅱ) HQHPA、Pd (Ⅱ) CuSO₄ HPA 等Wacker 类催化体系在烯烃氧化合成酮类物质中的应用; 对Pd (Ⅱ) LCoNO₂、PdCl₂(MeCN)₂ CuCl、Pd (OAc)₂ 吡啶、氟两相等非Wacker 类催化体系在烯烃氧化合成酮类物质中的应用也作了讨论。     

Solvent effects on catalytic activity of manganese porphyrins with cationic,anionic and uncharged meso substituents: Indirect evidence on the nature of active oxidant species

Oxidation of cyclohexene and styrene with sodium periodate and tetra‐n‐butylammonium periodate (TBAP) catalyzed by MnT(3‐MePy)P(OAc), MnT(4‐SO₃)PP(OAc) and MnTPP(OAc) has been studied in water, methanol, acetonitrile and dichloromethane as solvents. The results show significant dependence of the product distribution on the type of solvent and the electronic nature of the aryl substituents introduced at the porphyrin periphery. While the oxidation of cyclohexene and styrene in the presence of MnT(3‐MePy)P(OAc) and MnTPP(OAc) in water (also in methanol) gave the corresponding epoxides as nearly the sole product, performing the reactions in the presence of MnT(4‐SO₃)PP(OAc) yielded the products of allylic oxidation, cyclohexene‐2‐ol and cyclohexene‐2‐one and acetophenone as the major products. In the case of styrene, performing the reaction in the presence of MnT(4‐SO₃)PP(OAc), MnT(3‐MePy)P(OAc) and MnTPP(OAc) in acetonitrile gave a mixture of styrene oxide and acetophenone as the products. Under the same conditions, the oxidation of cyclohexene afforded cyclohexene oxide as approximately the exclusive product. Furthermore, the oxidation of olefins in dichloromethane gave the corresponding epoxide as the exclusive products. The product distributions observed in the protic and aprotic solvents were used to provide indirect evidence on the relative contribution and reactivity of high valent manganese oxo and periodato Mn(III) porphyrin species to the oxidation reactions.     

Highly selective C-H functionalization/halogenation of acetanilide

Highly regioselective C-H functionalization/halogenation of acetanilides to produce ortho-haloacetanilides was catalyzed by Pd(OAc)2 and Cu(OAc) 2 with CuX2 as the halogen source.     

Catalytic activity of Mn(III) and Fe(III) complexes of meso-tetra(n-propyl)porphyrin in oxidation of olefins: Meso-alkyl substituent in comparison with the alkenyl and aryl ones

Catalytic activity of Mn(III) and Fe(III) complexes of meso-tetra(n-propyl)porphyrin, MnT(n-Pr)P(X) and FeT(n-Pr)P(X) (X = Cl, SCN, OAc) in oxidation of olefins with tetra-n-butylammonium periodate at room temperature has been studied. The influence of different parameters including the molar ratio of catalyst to imidazole, type of counter ion (X) and oxidative stability of metalloporphyrins on the efficiency of the catalysts was investigated. The results of competitive oxidation of cis- and trans-stilbene suggest the presence of a high-valent Mn-oxo as the predominant oxidant species in equilibrium with a six coordinate complex, MnT(n-Pr)P(ImH)(IO₄) in the case of MnT(n-Pr)P(OAc). An unusual preference for trans-stilbene over cis-stilbene was observed in the reaction catalyzed by FeT(n-Pr)P(OAc). Control reaction indicated a significant cis- to trans-isomerization (81%) in oxidation of cis-stilbene catalyzed by FeT(n-Pr)P(OAc) which may explain the observed unusual cis to trans-stilbene oxide ratio. While oxidation of cyclooctene and styrene led to the exclusive formation of the corresponding epoxides, oxidation of cyclohexene gave 2-cyclohexe-1-ol and cyclohexene oxide as the products. However, the results of this study clearly demonstrate the key role played by the group substituted at the meso positions of metalloporphyrins on their catalytic activity, apart from the electron-donating or electron-withdrawing properties of the substituents.