冠醚化对双Schiff碱钴（Ⅱ）配合物催化氧化性能的影响

合成了冠醚化钴（Ⅱ）Ｓｃｈｉｆ碱配合物１ｃ及其相关类似物１ｂ，测定了它们的氧加合常数，考查了它们对异丙苯的催化氧化性能，并与未冠醚化的类似物１ａ作比较，讨论了１ｃ分子中的冠环对催化氧化性能的影响     

Schiff碱配合物催化过氧化氢氧化苯酚的动力学研究

按照文献方法合成了钴(Ⅱ)和铁(Ⅱ)Schiff碱配合物,研究了它们作为模拟过氧化物酶在缓冲溶液中以及在三种不同的表面活性剂(CTAB,Brij35,LSS)胶束中催化过氧化氢氧化苯酚的反应,结果表明：过氧化氢／配合物物质的量比和胶束微环境对金属配合物催化过氧化氢氧化苯酚的反应有明显的影响;本文所提出的Schiff碱金属配合物催化苯酚氧化反应的机理和动力学数学模型是合理的。     

组氨酸水杨醛Schiff碱铜（Ⅱ）配合物催化氧化β-紫罗兰酮的反应

组氨酸水杨醛Schiff碱铜（Ⅱ）配合物催化氧化β-紫罗兰酮的反应;β-紫罗兰酮;氧代-β-紫罗兰酮;Schiff碱;铜（Ⅱ）配合物;催化氧化     

Schiff碱配合物模拟酶催化性能的结构效应研究

研究了新型Schiff碱双锰及双铁配合物在模拟酶催化PhIO单加氧化环己烷反应及被PhIO氧化破坏反应中的结构效应.结果表明,随着这些配合物的环内空腔逐渐增大,其抗氧化稳定性、催化活性及催化反应产率依次降低.配合物中最佳螯合环为五元环.     

磁场对Schiff碱配合物模拟甲烷单加氧酶催化性能的影响

生命体中存在许多双金属酶 ,其结构和作用机制目前尚不清楚 ,为了模拟甲烷单加氧酶的催化作用 ,我们将催化活性较高的金属卟啉、稳定性较高的 Schiff碱及双核结构结合起来 ,设计合成了一系列“类卟啉型”Schiff碱双核配合物 ,并将这些双核配合物模拟酶催化亚碘酰苯 (Ph IO)单加氧化环己烷反应 ,发现其催化活性及抗氧化稳定性类似于四芳基金属卟啉 [1～ 3 ] ;还发现在模拟酶催化环己烷氧化反应中双核配合物中的两个金属离子间存在协同作用 [4 ] .外加磁场对一般热化学反应影响较小 [5～ 7] ,而在催化反应中的磁场效应更明显 [5,8] .为了较…     

松香基Schiff碱高分子金属配合物的制备及其对茴香油的催化氧化

以马来松香丙烯酸乙二醇酯(EGMRA)为原料与制备出的水合肼α-甲基丙烯酸-(4-醛基)-苯酯Schiff碱共聚制备松香基Schiff碱高分子物质(PS),然后将PS分别与铜离子和镍离子配位制备松香基Schiff碱高分子金属配位物PS-Cu及PS-Ni,并采用FTIR、1H-NMR、SEM及EDX对松香基Schiff碱高分子共聚物及其金属配位物进行表征,结果表明本研究提供的方法可成功制备出目标产物PS-Cu及PS-Ni。以H_2O_2为氧源、PS-Cu及PS-Ni为催化剂,对茴香油的催化氧化进行研究,在PS-Cu存在的条件下,茴香油的转化率为70%,高于空白试验组的转化率(47%);但是,在PS-Ni存在的条件下,茴香油的转化率却低于空白试验组;表明松香基Schiff碱共聚高分子铜离子配合物催化氧化茴香油的效果要优于镍离子配合物。     

双齿单Schiff碱钴、锰配合物的合成、表征及催化氧化性能的研究

合成了单S chiff碱配体水杨醛缩邻甲苯胺（^1L）、5-溴水杨醛缩对氯苯胺（^2L）、5-溴水杨醛缩对甲苯胺（3^L）、水杨醛缩对硝基苯胺（^4L）、水杨醛缩对甲苯胺（^5L）、水杨醛缩对氯苯胺（^6L）及其钴、锰配合物，并用MS、^3HNMR、IR以及元素分析等测试技术予以表征，以钴配合物为催化剂活化分子氧氧化环巳烯，高选择性地得到烯丙位的氧化产物；以锰配合物为催化剂、NaOcl为氧化剂催化苯乙烯的环氧化，主要产物为苯乙烯环氧化物。     

非对称Schiff碱过渡金属配合物模拟酶催化烯烃环氧化(Ⅰ)

研究了温和条件下以亚碘酰苯为氧源,非对称性的和对称性的Mn(Ⅲ)Schiff碱配合物[Mn(Ⅲ)(CBP－phen－Xsal)Cl,X=H,Cl,Br,NO₂,CH₃,OCH₃]和[Mn(Ⅲ)(CBP－R－CBP)Y,R=CH₂CH₂－,－CH(CH₃)CH₂－,－C₆H₄－;Y=Cl,OCH₃]催化非官能性烯烃苯乙烯、环己烯和α-甲基苯乙烯的环氧化反应.结果表明,非对称配合物Mn(Ⅲ)(CBP－phen－Xsal)Cl是一个良好的催化非官能性烯烃环氧化反应的催化剂体系;中心金属离子Mn(Ⅲ)的电子结合能越小,催化环氧化效果越好;对上述3种烯烃环氧化物最好收率分别达到73％、100％和92％.     

Schiff 碱双核配合物的磁性及催化性能的研究

This paper reports the catalytic properties of “porphyrin-like” Schiff base mononuclear complexes MH₂L {M=Mn(Ⅱ), Fe(Ⅲ)Cl, Cr(Ⅲ)Cl, Cu(Ⅱ), Co(Ⅱ), Ni(Ⅱ), Zn(Ⅱ); L=bis[N, N′-ethylene-2, 2′-(phenylmethylene)bis(3,4-dimethylpyrrole-5-aldimino)]} and dinuclear complexes MnML [M=Mn(Ⅱ), Fe(Ⅲ)Cl, Cr(Ⅲ)Cl, Cu(Ⅱ), Co(Ⅱ), Ni(Ⅱ), Zn(Ⅱ)] for cyclohexane monooxygenation with PhIO and magnetic properties of the dinuclear complexes. The magnetic investigations (4～300 K) of the dinuclear complexes revealed that their antiferromagnetic spin exchange with J ranged from -10.49 to -0.482 cm^-1 except MnZnL and antiferromagnetic spin exchange decreased in the following order: Mn^Ⅱ-Cu^Ⅱ > Mn^Ⅱ-Ni^Ⅱ > Mn^Ⅱ-Mn^Ⅱ > Mn^Ⅱ-Fe^Ⅲ > Mn^Ⅱ-Co^Ⅱ > Mn^Ⅱ-Cr^Ⅲ. The results of catalyzed oxidation of cyclohexane indicated that the catalytic property of the dinuclear complex was better than that of the corresponding mononuclear complex. It was found that there was the synergism decreased in the order: Mn-Fe > Mn-Cr > Mn-Cu > Mn-Mn > Mn-Co> Mn-Ni > Mn-Zn. It seems that this synergism increases with the increase of the number of unpaired d electrons and the magnetic exchange between the two metals in these dinuclear complexes.     

Schiff碱单核及双核配合物拟酶催化性能的研究

系统地研究了新型Schiff碱单核及双核配合物在拟酶催化PhIO单加氧化环己烷反应中的催化性能.结果表明,双核配合物MnML{M=Mn(Ⅱ),Fe(Ⅲ)Cl,Cr(Ⅲ)Cl,Cu(Ⅱ),Co(Ⅱ),Ni(Ⅱ),Zn(Ⅱ);L=双[N,N'亚乙基2,2'(苯亚甲基)二(3,4二甲基吡咯5醛缩亚胺)]}的催化活性比对应的单核配合物MnH₂L与MH₂L之混合物的催化活性高.因此,我们认为在双核配合物中两金属离子间存在协同作用,并发现这种协同作用一般随双核配合物中成单d电子数增加而增大.     

穴状Schiff碱配合物［Gd(NO3)·L］(NO3)2的晶体结构

A new mononuclear gadolinium complex ［Gd(NO₃)·L］(NO₃)₂ of Schiff base cryptand was obtained by condensation of tris (2-aminoethyl)amine with 2,6-diformyl phenol in template procedure. The complex was characterized by elemental analysis, IR, and x-ray single crystal diffraction analysis. Gadolinium is nine-coordinate in trigonal tricapped prism with five oxygen atoms from three phenols and a bidentate nitrate group, and four nitrogen atoms from three imino C=N bonds and a tertiary amine in the cryptand. The complex crystallized in triclinic system space group P1, a=1.0839(2) nm, b=1.2600(4) nm, c=1.7595(4) nm, α=82.09(2)°, β=89.22(2)°, γ=84.06(2)°， V=2.367(2) nm³, Z=2.     

N-羟基-N-苯基-2-吡啶甲酰胺钴配合物的合成及均相催化乙苯的氧化反应

近年来,在催化氧化反应领域,人们一直试图用价廉易得的氧作氧化剂,在较温和的条件下催化烃类氧化,以得到价值更高的含氧化合物．研究新的活化分子氧的高活性催化剂成为化学家追求的重要目标之一［１～４］．在各类催化剂中,金属卟啉类［５,６］和金属席夫碱类［...     

制备因素对Ni—Co—O复合氧化物结构及氧化活性的影响

用共沉淀法和机械混合锻烧法制备了Ｎｉ－Ｃｏ－Ｏ复合氧化物催化剂。用ＴＰＲ、ＸＲＤ氧化活性评价等实验手段对催化剂进行了考察。结果表明不同方法制得的复合氧化物呈现不同的催化行为。共沉淀的ｐＨ值的高低及焙烧温度对催化剂的氧化活有较大影响，尖晶石型复合相ＮｉＣｏ２Ｏ４可能是提高催化剂氧活性的活性相。     

PREPARATION AND CATALYTIC PROPERTIES OF POLYMER-BOUND SCHIFF BASE TERNARY COMPLEXES

ABSTRACT

The polymer-bound Schiff base ternary cobalt complexes (PS-SalPhe-Co-L (L=Phen, Bipy and 8HQ)) have been prepared from the polymer bound Schiff base ligand, cobalt salt and the second ligand, such as 1,10-phenanthroline(phen), 2,2′-bipyridyl(bipy) and 8-quinolinol(8HQ). The polymer-bound Schiff base ternary cobalt complexes were characterized by the infrared spectra and ICP-AES. The catalytic activity of the complexes has been studied in aerobic epoxidation of long-chain linear aliphatic olefins. It showed that 1-octene or 1-decene can be directly oxidized by molecular oxygen catalyzed by PS-SalPhe-Co-L (L=Phen, Bipy and 8HQ), which afford the 1,2-epoxy alkane.     

二氧化钛负载氧化物催化剂上CO的氧化反应

对浸渍法和共沉淀法制备以的各种ＴｉＯ２负载氧化物催化剂进行了活性组分的筛选,结果发现,两种方法得到的ＣｕＯ催化剂均具有优良的ＣＯ氧化催化性能。在此基础上,考察不同ＴｉＯ２载体,活性组分含量以及催化剂焙烧温度对其催化能力的影响。结果表明,具有高比表面、大孔体积的ＴｉＯ２载体负功的ＣｕＯ催化剂具有较好的催化性能,活性组分ＣｕＯ的最佳含量范围在１０％～１５％之间,催化剂最佳焙烧温度为４００℃。     

SYNTHESIS AND CATALYTIC PROPERTY OF POLYSTYRENE SUPPORTED PHENYLALANINE SCHIFF BASE COMPLEX OF Mn（Ⅱ） IN AEROBIC OXIDATION OF CYCLOHEXENE

The polystyrene supported phenylalanine Schiff base complex of Mn(Ⅱ)(PS-Sal-Phe-Mn)was prepared with chloromethylated styrene polymer beads, 2,4-dihydroxybenzaldehyde,L-phenylalanine and manganese(Ⅱ)acetate tetrahyrate., The polymeric ligand and the complex were characterized by FT-IR,, small area X-ray photoelectron spectroscopy(XPS), and ICP-AES. In the presence of the manganese complex, cyclohexene(1)was effectively oxidized by molecular oxygen without reductant. The major products of the reaction were 2-cyclohexen-1-ol(2),2-cyclohexen-1-one(3)and 2-cyclohexen-1- hydroperoxide(4), which was different with typical oxidation of cyclohexene. The influence of reaction temperature and additive for oxidation had been studied. The selectivity of 2-cyclohexen-l-hydroperoxide varied with reaction time and different additives. The mechanism of cyclohexene oxidation had also been discussed.     

Schiff碱配合物的研究——Ⅸ.表面Schiff碱配合物对H_2O_2分解的催化作用

制备了两种表面Schiff碱及其Cu~(2+)、Co~(2+)、Ni~(2+)、Zn~(2+)配合物,考察了它们对H_2O_2分解的催化性能,其活性顺序为:Co~(2+)>Cu~(2+)>Ni~(2+)>Zn~(2+),且与金属离子氧化还原电位有关。溶液的pH值增加有利于催化反应,有机配体的加入则对反应有所抑制。     

SYNTHESIS AND CATALYTIC PROPERTY OF POLYSTYRENE SUPPORTED GLUTAMIC ACID SCHIFF BASE COMPLEX OF Mn(Ⅱ)IN AEROBIC OXIDATION OF CYCLOHEXENE

The polystyrene supported glutamic acid Schiff base complex of Mn (Ⅱ) (PS-Sal-Glue-Mn) was prepared with chloromethylated styrene polymer beads,2,4-dihydroxybenzaldehyde, L-glutamic acid and manganese (Ⅱ) acetate tetrahyrate. The polymeric ligand and the complex were characterized by FT-IR, small area X-ray photoelectron spectroscopy (XPS) and ICP-AES. In the presence of the manganese complex, cyclohexene (1) was effectively oxidized by molecular oxygen without reductant. The major products of the reaction were 2-cyclohexen-1-ol (2), 2-cyclohexen-1-one (3) and 2-cyclohexen-1- hydroperoxide (4), which was different with typical oxidation of cyclohexene. The influence of reaction temperature and additive for oxidation had been studied. The selectivity of 2-cyclohexen-1-hydroperoxide varied with reaction time and different additives. The mechanism of cyclohexene oxidation had also been discussed.     

Schiff碱配合物的研究——Ⅸ.表面Schiff碱配合物对H2O2分解的催化作用

制备了两种表面Schiff碱及其Cu²⁺、Co²⁺、Ni²⁺、Zn²⁺配合物,考察了它们对H₂O₂分解的催化性能,其活性顺序为:Co²⁺>Cu²⁺>Ni²⁺>Zn²⁺,且与金属离子氧化还原电位有关。溶液的pH值增加有利于催化反应,有机配体的加入则对反应有所抑制。     

SYNTHESIS AND CATALYTIC PROPERTY OF POLYSTYRENE SUPPORTED GLUTAMIC ACID SCHIFF BASE COMPLEX OF Mn（ Ⅱ ） IN AEROBIC OXIDATION OF CYCLOHEXENE

The polystyrene supported glutamic acid Schiff base complex of Mn （ Ⅱ ） （PS-Sal-Glue-Mn） was prepared with chloromethylated styrene polymer beads, 2,4-dihydroxybenzaldehyde, L-glutamic acid and manganese （ Ⅱ ） acetate tetrahyrate. The polymeric ligand and the complex were characterized by FT-IR, small area X-ray photoelectron spectroscopy （XPS） and 1CP-AES. In the presence of the manganese complex, cyclohexene （1） was effectively oxidized by molecular oxygen without reductant. The major products of the reaction were 2-cyclohexen-l-ol （2）, 2-cyclohexen-l-one （3） and 2-cyclohexen-1- hydroperoxide （4）, which was different with typical oxidation of cyclohexene. The influence of reaction temperature and additive for oxidation had been studied. The selectivity of 2-cyclohexen-1-hydroperoxide varied with reaction time and different additives. The mechanism of cyclohexene oxidation had also been discussed.