钾镁氯化物(硫酸盐)与脲、水体系的溶度研究

报导了KCl-MgCl2-CO(NH2)2-H2O和K2SO4-MgSO4-CO（NH2）2-H2O两个四元体系在25℃时的溶度及其饱和溶液的折光率、密度，相应的溶度图和组成-折光率、组成-密度图．前一体系中形成3个三元化合物：MgCl2·4CO（NH2）2·2H2O、MgCl2·CO（NH2）2·4H2O和KCl·MgCl2·6H2O溶度盐份图由9支共饱线、4个四元无变点组成．四元体系的水量图、性质-组成图有类似的变化．后一体系中有2个异成份溶解化合物MgSO4·CO（NH2）2·2H2O和K2SO4·MgSO4·6H2O形成，溶度等温图由7支双饱溶度线、3个四元无变点组成．对两个体系相图的相似性和差异点进行了讨论．     

H_2O_2氧化N_2生成N_2O和H_2O机理的研究

采用量子化学计算方法研究了Ｈ２Ｏ２ 氧化Ｎ２ 生成Ｎ２Ｏ 和Ｈ２Ｏ 的机理．结果发现, Ｈ２Ｏ２ 氧化Ｎ２ 先通过１ 个四元环过渡态形成中间体Ｈ２Ｎ２Ｏ２ 分子,Ｈ２Ｎ２Ｏ２ 再通过一个五元环过渡态形成Ｎ２Ｏ和Ｈ２Ｏ．根据计算得到的每步反应的活化能,得知Ｈ２Ｏ２ 氧化Ｎ２ 生成中间体Ｈ２Ｎ２Ｏ２ 分子是整个反应的控制步骤．     

硫化合物与H2O2在非催化反应中的非线性行为

硫化学反应中的非线性是近年来非线性化学研究的热点之一，我们注意到CU（11催化剂存在时H202氧化KSCN山、N。。S。0开］出现振荡或复杂振荡现象，但这两个反应的机理研究尚处在不成熟或模糊阶段＊‘1，由于K盯N、＊。。a0。和优（＊H小氧化过程有多种价态的变化，Cu（11）催化     

普钙-脲-水复合肥料体系的等温溶度研究

从发展复合肥料出发,研究了ＣａＳＯ－Ｃａ（Ｈ２ＰＯ４）２Ｈ２Ｏ体系及其三元边界体系Ｃａ（Ｈ２ＰＯ４）２－ＣＯ（ＮＨ２）２－Ｈ２Ｏｄ ２５℃时的等温溶度,三元体系中形成一个新化合物Ｃａ（Ｈ２ＰＯ４）２。ＣＯ（ＮＨ２）２。四元体系溶 度图可以指导商品普钙磷肥转化为含各合复肥。     

双丙炔醇酯类化合物的合成与表征

合成了5个新的二丙炔醇酯类化合物[(CO2CH2C≡CH)2(1),CH2(CO2CH2C≡CH)2,(2),(CH2CO2CH2C≡CH2)(3),(CHCO2CH2C≡CH)2,(4),C6H4-1,4-(CO2CH2C≡CH)2,(5)]，并对其进行了C／H，IR和^1H NMR等表征。     

中心为氨基、末端为硝基的苯乙炔树枝状分子的合成

将固定相合成与“收敛/发散”方法相结合,合成了第一、二代苯乙炔树枝状分子.通过Heck-Cassar-Sonogashira-Hagihara偶联反应,将其中心和末端分别修饰上供电子的氨基和拉电子的硝基,得到第一、二代中心为氨基、末端为硝基的苯乙炔树枝状分子NH₂-G1-(NO₂)₂和NH₂-G2-(NO₂)₄.用傅里叶变换红外光谱跟踪了整个固定相合成过程.苯乙炔树枝状分子的紫外-可见吸收光谱呈现出规律性变化.     

1,3-二碘六氟丙烷的电子转移反应

在四醋酸铅的催化下,二氟二碘甲烷(CF2I2,1)与四氟乙烯加成生成1,3-二碘六氟丙烷(ICF2CF2CF2I,3).3与烯烃、炔烃和丙二酸二乙酯阴离子发生电子转移反应。     

Redox-active p-quinone-based Bis(pyrazol-1-yl)methane ligands: synthesis and coordination behaviour

The synthesis, structural characterisation and coordination behaviour of mono- and ditopic p-hydroquinone-based bis(pyrazol-1-yl)methane ligands is described (i.e., 2-(pz2CH)C6H3(OH)2 (2a), 2-(pz2CH)-6-(tBu)C6H2(OH)2 (2b), 2-(pz2CH)-6-(tBu)C6H2(OSiiPr3)(OH) (2c), 2,5-(pz2CH)2C6H2(OH)2 (4)). Ligands 2a, 2b and 4 can be oxidised to their p-benzoquinone state on a preparative scale (2a ox, 2b ox, 4 ox). An octahedral Ni II complex [trans-Ni(2c)2] and square-planar Pd II complexes [Pd2bCl2] and [Pd2b ox Cl2] have been prepared. In the two Pd II species, the ligands are coordinated only through their pyrazolyl rings. The fact that [Pd2bC12] and [Pd2b oxC12] are isolable compounds proves that redox transitions involving the p-quinone substituent are fully reversible. In [Pd2b oxCl2], the methine proton is highly acidic and can be abstracted with bases as weak as NEt(3). The resulting anion dimerises to give a dinuclear macrocyclic Pd II complex, which has been structurally characterised. The methylated ligand 2-(pz2CMe)C6H3O2 (11 ox) and its Pd II complex [Pd11 oxCl2] are base-stable. A new class of redox-active ligands is now available with the potential for applications both in catalysis and in materials science.     

若干线型Mo-Fe-S簇合物红外光谱及其与结构关系的研究

对若干线型Mo一Fe一S簇合物[Cl2FeS2MoS2FeCl2][-2](1)、[S2MoS2FeCl2]^2^-(2)、[S2MoS2Fe(SPh)2][2-](3)、[S2MoS2FeS2Fe(SPh)2][3-](4)、[S2MoS2FeS2MoS2][3-](5)、Cl2FeS2FeCl2][2-](6)、[(PhS)2FeS2Fe(SPh)2][2-](7)的红外光谱进行了研究。通过比较它们的特征频率、结构参数和金属原子的氧化态,对νMo-St、νMo-SbνFe-Sb、νFe-SPh、νFe-Cl进行了归属。并对δS-Mo-S的归属作了初步探讨。文中讨论了MoS2Fe单元中Mo原子对νFe-Sb的影响, 通过振动频率与结构关系的研究揭示其内在联系及规律性。对两条途径的亲电诱导效应进行了讨论, 并提出一个能定性标志Fe→Mo电荷迁移大小的有用参数Δν值。     

Betaine-induced assembly of neutral infinite columns and chains of linked silver(I) polyhedra with embedded acetylenediide

Ten polymeric silver(I) double salts containing embedded acetylenediide: [(Ag2C2)2(AgCF3CO2)9(L1)3] (1), [(Ag2C2)2(AgCF3CO2)10(L2)3]H2O (2), [(Ag2C2)(AgCF3CO2)4(L3)(H2O)]0.75 H2O (3), [(Ag2C2)(1.5)(AgCF3CO2)7(L4)2] (4), [(Ag2C2)(AgCF3CO2)7(L5)2(H2O)] (5), [(Ag2C2) (AgC2F5CO2)7(L1)3(H2O)] (6), [(Ag2C2)(AgCF3CO2)7(L1)3(H2O)]2 H2O (7), [(Ag2C2)(AgC2F5CO2)6(L3)2] (8), [(Ag2C2)2(AgC2F5CO2)12(L4)2(H2O)4]H2O (9), and [(Ag2C2)(AgCF3CO2)6(L3)2(H2O)]H2O (10) have been isolated by varying the types of betaines, the perfluorocarboxylate ligands employed, and the reaction conditions. Single-crystal X-ray analysis has shown that 1-4 all have a columnar structure composed of fused silver(I) double cages, with C2(2-) species embedded in its stem and an exterior coat comprising anionic and zwitterionic carboxylates. For 5 and 6, single silver(I) cages are linked into a beaded chain through both types of carboxylate ligands. In 7, two different coordination modes of L1 connect the silver(I) polyhedra into a chain. For 8, the mu(2)-O,O' coordination mode of L3 connects the silver(I) double cages into a chain. Compound 9 exhibits a two-dimensional architecture generated from the cross-linkage of double cages by C2F5CO2-, L4, and [Ag2(C2F5CO2)2] units. Similar to 9, 10 is also a two-dimensional structure, which is formed by connecting the chains of linked double cages through [Ag2(CF3CO2)2] bridging.     

二氟二碘甲烷与乙烯基乙醚的反应及其产物的化学转化

二氟二碘甲烷(CF2I2,1)与乙烯基乙醚和Na2S2O4在DMSO和乙醇的混合溶剂中反应得3,3-二氟-3-碘丙醛的乙缩醛[ICF2CH2CH(OEt)2](3).3在锌粉的作用下发生偶联反应生成二缩醛[(EtO)2CHCH2CF2CF2CH2CH(OEt)2](5)。缩醛3或5与烯醇硅醚在SnCl4作用下发生交叉偶联反应。3在锌粉或保险粉的引下与烯醇硅醚发生加成反应。3和5分别转化成硫缩醛ICF2CH2CH(SR)2(13),(RS)2CHCH2CF2CF2CH2CH(SR)2(14)或O,S-缩醛。13消HI得1,1-二氟乙烯衍生物。     

THE ADSORPTION OF OXYGEN OVER ThO_2-BaF_2 CATALYST

IntroductionInthcsclcctivcoxidationofalkanes.suchas'theoxidativccouplingofmcthanc(0CM)andthcoxidativcdch}'drogenationofcthanc(0DE)t0prcparccth}'lene.bothoxidcionsofthelatticeandtheox}'genspeciesovercataIystsuffocepla}'animportantrole.Althoughcxtcnsivcinvcstigationshavcbeengivcntothecharactcrizationofox}'gcnspccicsandthcreactionofox}'gcnspecicsx`ithalkanes,itisstilldifficulttosayt`hichoncsofox}'gcnspcciesarcthcactivcspecicsinthcactivation0falkancs.bccauscthenaturcofcatal}'stsandthecxperimcntc…     

基于锌(Ⅱ)Schiff碱构筑模块和6-羧基吡啶-2-甲醇的3d-4f异金属四核簇合物的荧光和磁弛豫性质

用溶剂热方法合成了2个新的3d-4f异金属四核簇合物：[Zn₂Ln₂（salen）₂（CO₂PyCH₂O）₂（MeOH）2]（ClO₄）₂·2MeOH（Ln=Dy（1）,Tb（2）;H₂salen=N,N'-双（3-甲氧基水杨基）-1,3-二氨基丙烷;HCO₂PyCH₂OH=6-羧基吡啶-2-甲醇）。它们是由锌（Ⅱ）Schiff碱构筑模块和6-羧基吡啶-2-甲醇辅助配体组装而成的Zn-Ln₂-Zn型簇合物。磁性测量表明稀土离子间存在铁磁性相互作用。Zn₂Dy₂配合物1在2 000 Oe直流磁场下显示出磁弛豫行为;而Zn₂Tb₂配合物2不但有磁场导致的磁弛豫行为,而且还具有荧光性质。     

一种锰的超分子化合物的制备、结构及非线性光学 性质研究

用MnSO4·H2O,KSCN,六次甲基四胺(HMTA)制备出超分子化合物[Mn(NCS)2(H2O)2(HMTA)2][Mn(NCS)2(H2O)4](H2O)2,并测定了其晶体结构。该化合物由[Mn(NCS)2(H2O)2(HMTA)2],[Mn(NCS)2(H2O)4]和H2O三部分组成,每一个HMTA配体中仅有一个N原子与Mn原子配位,剩余的3个N分别与[Mn(NCS)2(H2O)4]中的H2O及结晶H2O之间形成氢键。[Mn(NCS)2(H2O)2(HMTA)2]和[Mn(NCS)2(H2O)4]之间通过N…H—O氢键边接成无限延伸的线性长链,链与链、以及链和结晶H2O之间通过七种形式的氢键构成三维结构的超分子。用Z-扫描法测定该化合物在DMF溶液中的三阶非线性光学性质,发现它具有自聚焦效应,三阶非线性折射系数n2=9.52×10^-9m^2·W^-1,非线性极化率χ^(3)=3.41×10^-12esu.     

Binding N2, N2H2, N2H4, and NH3 to transition-metal sulfur sites: modeling potential intermediates of biological N2 fixation

In the quest for low-molecular-weight metal sulfur complexes that bind nitrogenase-relevant small molecules and can serve as model complexes for nitrogenase, compounds with the [Ru(PiPr(3))('N(2)Me(2)S(2)')] fragment were found ('N(2)Me(2)S(2)'(2-)=1,2-ethanediamine-N,N'-dimethyl-N,N'-bis(2-benzenethiolate)(2-)). This fragment enabled the synthesis of a first series of chiral metal sulfur complexes, [Ru(L)(PiPr(3))('N(2)Me(2)S(2)')] with L=N(2), N(2)H(2), N(2)H(4), and NH(3), that meet the biological constraint of forming under mild conditions. The reaction of [Ru(NCCH(3))(PiPr(3))('N(2)Me(2)S(2)')] (1) with NH(3) gave the ammonia complex [Ru(NH(3))(PiPr(3))('N(2)Me(2)S(2)')] (4), which readily exchanged NH(3) for N(2) to yield the mononuclear dinitrogen complex [Ru(N(2))(PiPr(3))('N(2)Me(2)S(2)')] (2) in almost quantitative yield. Complex 2, obtained by this new efficient synthesis, was the starting material for the synthesis of dinuclear (R,R)- and (S,S)-[micro-N(2)[Ru(PiPr(3))('N(2)Me(2)S(2)')](2)] ((R,R)-/(S,S)-3). (Both 2 and 3 have been reported previously.) The as-yet inexplicable behavior of complex 3 to form also the R,S isomer in solution has been revealed by DFT calculations and (2)D NMR spectroscopy studies. The reaction of 1 or 2 with anhydrous hydrazine yielded the hydrazine complex [Ru(N(2)H(4))(PiPr(3))('N(2)Me(2)S(2)')] (6), which is a highly reactive intermediate. Disproportionation of 6 resulted in the formation of mononuclear diazene complexes, the ammonia complex 4, and finally the dinuclear diazene complex [micro-N(2)H(2)[Ru(PiPr(3))('N(2)Me(2)S(2)')](2)] (5). Dinuclear complex 5 could also be obtained directly in an independent synthesis from 1 and N(2)H(2), which was generated in situ by acidolysis of K(2)N(2)(CO(2))(2). Treatment of 6 with CH(2)Cl(2), however, formed a chloromethylated diazene species [[Ru(PiPr(3))('N(2)Me(2)S(2)')]-micro-N(2)H(2)[Ru(Cl)('N(2)Me(2)S(2)CH(2)Cl')]] (9) ('N(2)Me(2)S(2)CH(2)Cl'(2-) =1,2-ethanediamine-N,N'-dimethyl-N-(2-benzenethiolate)(1-)-N'-(2-benzenechloromethylthioether)(1-)]. The molecular structures of 4, 5, and 9 were determined by X-ray crystal structure analysis, and the labile N(2)H(4) complex 6 was characterized by NMR spectroscopy.     

芥子气模拟剂2-氯乙基乙基硫醚的光催化降解

利用连续流动微反、原位红外和GC/MS等手段考察了芥子气模拟剂2-氯乙基乙基硫醚（2-CEES）在P25 TiO2上的光催化降解反应,证实CO2和H2O是这个反应的最终产物.详细的跟踪分析表明,除了CO2和H2O外,在反应的气相混合物中可检测到C2H4、CH3CHO、CH4、CO、HCl和H2S；少量小分子的羧酸、醚和砜；微量C2H5SC2H5、C2H5S2C2H5、C2H5SC2H4Cl和CH2ClCH2Cl等中间产物;在反应后的催化剂表面可检测到C2H5S2C2H5、C2H5SC2H4OH、C4H9S2C2H5和C2H5S2C2H4OH、等物.根据这些结果提出了2-CEES光催化降解的反应机理,推断2-CEES的光催化降解涉及脱氯、C－S键断裂、有机硫化物光聚合和裂解等复杂过程最终转化为CO2和H2O.认为各种硫物种在表面的积聚引起了催化剂的缓慢失活.     

离子型有机锡化合物的合成及其生物活性

利用有机锡卤化物与有机酸在有机胺存在下反应合成了一系列离子型有机锡化合物,分子通式为[HNR3][(PhCH2)3Sn(μ2-SCH2COO)Cl]、[HNR3][Ph3Sn)3(O2CCH2CO2)2]·CH3CH2OH和[HNR3] [MeCy2ClSnO2CCH2CO2SnClCy2Me]。化合物的体外抗肿瘤、杀菌和杀螨活性测试结果表明,部分化合物具有很好的生物活性。[HNR3][(Ph3Sn)3(O2CCH2CO2)2]·CH3CH2OH和[HNR3] [MeCy2ClSnO2CCH2CO2SnClCy2Me]配合物对人肺癌细胞株A-549、结肠癌细胞株HCT-8和肝癌细胞株Bel-7402的抑制率约为90%,[HNR3][MeCy2ClSnO2CCH2CO2SnClCy2Me]配合物对小麦赤霉、番茄早疫、芦笋茎枯、苹果轮纹、花生褐斑的杀死率都为100%,配合物[HNR3] [MeCy2ClSnO2CCH2CO2SnClCy2Me]的杀螨活性致死率大于90%。     

乙烷与CO2制乙烯反应的热力学和动力学研究

乙烷与ＣＯ２的主要反应及其热力学研究表明，乙烷与ＣＯ２反应很复杂，提高ＣＯ２氧化乙烷脱氢生成乙烯的选择，关键在一催化剂的开发；ＣＯ２不但可提高乙灶脱氢制乙烯的热力学平衡转化率，而且可与催化剂表面的积碳发生反应，延长催化剂的使用寿命。研究了催化剂上乙烷与ＣＯ２制乙烯反应的动力学，确定了ＣＯ２氧化乙烷脱氢反应的动力学方程及参数，表明乙烷与ＣＯ２制乙烯的反应速度比乙烷热裂解制乙烯的反应速度要大得多。     

Hydrogenation studies involving halobis(phosphine)-rhodium(I) dimers: use of parahydrogen induced polarisation to detect species present at low concentration

Reaction of [RhCl(PPh3)2]2 with parahydrogen revealed that the binuclear dihydride [Rh(H)2(PPh3)2mu-Cl)2Rh(PPh3)2] and the tetrahydride complex [Rh(H)2(PPh3)2(mu-Cl)]2 are readily formed. While magnetisation transfer from free H2 into both the hydride resonances of the tetrahydride and [Rh(H)2Cl(PPh3)3] is observable, neither transfer into [Rh(H)2(PPh3)2(mu-Cl)2Rh(PPh3)2] nor transfer between the two binuclear complexes is seen. Consequently [Rh(H)2(PPh3)2(mu-Cl)]2 and [Rh(H)2(PPh3)2(mu-Cl)2Rh(PPh3)2] are not connected on the NMR timescale by simple elimination or addition of H2. The rapid exchange of free H2 into the tetrahydride proceeds via reversible halide bridge rupture and the formation of [Rh(H)2(PPh3)2(mu-Cl)RhCl(H)2(PPh3)2]. When these reactions are examined in CD2Cl2, the formation of the solvent complex [Rh(H)2(PPh3)2(mu-Cl)2Rh(CD2Cl2)(PPh3)] and the deactivation products [Rh(Cl)(H)PPh3)2(mu-Cl)(mu-H)Rh(Cl)(H)PPh3)2] and [Rh(Cl)(H)(CD2Cl2)(PPh3)(mu-Cl)(mu-H)Rh(Cl)(H)PPh3)2] is indicated. In the presence of an alkene and parahydrogen, signals corresponding to binuclear complexes of the type [Rh(H)2(PPh3)2(mu-Cl)(2)(Rh)(PPh3)(alkene)] are detected. These complexes undergo intramolecular hydride interchange in a process that is independent of the concentration of styrene and catalyst and involves halide bridge rupture, followed by rotation about the remaining Rh-Cl bridge, and bridge re-establishment. This process is facilitated by electron rich alkenes. Magnetisation transfer from the hydride ligands of these complexes into the alkyl group of the hydrogenation product is also observed. Hydrogenation is proposed to proceed via binuclear complex fragmentation and trapping of the resultant intermediate [RhCl(H)2PPh3)2] by the alkene. Studies on a number of other binuclear dihydride complexes including [(H)(Cl)Rh(PMe3)2(mu-H)(mu-Cl)Rh(CO)(PMe3)], [(H)2Rh(PMe3)2(mu-Cl)2Rh(CO)(PMe3)] and [HRh(PMe3)2(mu-H)(mu-Cl)2Rh(CO)(PMe3)] reveal that such species are able to play a similar role in hydrogenation catalysis. When the analogous iodide complexes [RhIPPh3)2]2 and [RhI(PPh3)3] are examined, [Rh(H)2(PPh3)2(mu-I)2Rh(PPh3)2], [Rh(H)2(PPh3)2(mu-I)]2 and [Rh(H)2I(PPh3)3] are observed in addition to the corresponding binuclear alkene-dihydride products. The higher initial activity of these precursors is offset by the formation of the trirhodium phosphide bridged deactivation product, [[(H)(PPh3)Rh(mu-H)(mu-I)(mu-PPh2)Rh(H)(PPh3)](mu-I)2Rh(H)2PPh3)2]     

金属有机多齿配体配位化学: 双核化合物的形成促使铁卡宾键的稳定化

单核物MXn[MXn=HgCl2,HgI2,CdCl2,K2Zn(SCN)4]与1,3-二硫铁卡宾化合物Fe(CO)2.(Ph2PPy)2[CS2C2(CO2Me)2]反应生成稳定的双核铁卡宾配合物FeM(μ-Ph2PPy)2[CS2C2.(CO2Me)2](CO2)2X2(Ph2PPy为2-二苯基膦基吡啶)。这些配合物为IR,^3^1P NMR, 及元素分析所证实。