亚乙基桥联双茚锆、铪配合物的合成及催化丙烯选择性齐聚研究:茚环3-位取代基的影响

设计并合成了12个亚乙基桥联双茚类锆、铪配合物meso-/rac-1～7[ansa-C₂H₄-(3-R-4,7-Me₂-C₉H₃)₂MCl₂:M=Zr R=ⁿBu (meso-/rac-1),ⁱPr (meso-2),CH₂Cy (meso-/rac-3),Bn (meso-/rac-4),CH₂C₆H₄(4-CH₃)(meso-/rac-5);M=Hf,R=CH₂C₆H₄(4-CH₃)(meso-/rac-7);ansa-C₂H₄-{2-Me-3-Bn-5,6-[1,3-(CH₂)₃]C₉     

氰基桥联铁钴链状配合物的结构与磁性

利用三氰基构筑单元(Bu₄N)[Fe(PzTp)(CN)₃](PzTp=tetrakis(pyrazolyl)borate)和(E)-1-苯乙烯基-1H-咪唑(Bzi),合成了2例氰基桥联的铁钴链状配位聚合物。单晶X射线衍射表明,配合物[Fe(PzTp)(CN)₃]₂[Co(Bzi)₄]₂(ClO₄)₂·H₂O (1)为方波形单链结构,而配合物[Fe(PzTp)(CN)₃]₂[Co(Bzi)₂]·CH₃OH (2)则形成含有甲醇溶剂分子的双“之”字形双链结构。磁学研究显示,配合物1在360 K左右显示出热诱导的自旋转变,而配合物2在大约200 K显示出溶剂诱导的两步自旋转变。变温红外光谱证实了热诱导的金属间电荷转移行为。此外,光磁实验显示,当用808和532 nm的光交替照射时,1显示出可逆的光诱导电荷转...     

两个含N-皮考林酰肼铁配合物的合成和结构表征

合成了含N-乙酰皮考林酰肼(简写为Haphz)的铁配合物[Fe₂(aphz)₂(μ-CH₃O)₂Cl₂]·CH₃OH(1,C₁₉H₂₆Cl₂Fe₂N₆O₇,Mr=633.06)和含N-苯甲酰皮考林酰肼(简写为Hphphz)的铁配合物Fe(phphz)Cl₂(2,C₁₃H₁₀Cl₂FeN₃O₂,Mr=366.99).2个配合物均属三斜晶系,空间群为P     

阳离子取代基对离子液体气相色谱固定相保留性能的影响

以双-三氟甲烷磺酰亚胺离子（［NTf₂］^-）、三氟甲基磺酸根离子（［TFO］^-）和六氟磷酸根离子（［PF₆］^-）为阴离子,合成了含有丙基、丁基、壬基、乙苯基或氰甲基等阳离子取代基的聚合乙烯基咪唑基离子液体固定相,制备了13种离子液体石英毛细管色谱柱。考察了离子液体固定相结构与色谱柱McReynolds常数、热稳定性和测试化合物保留行为之间的构效关系,研究了阳离子取代基对固定相保留性能的影响规律;同时考察了测试化合物保留指数随温度变化的规律。结果表明,所合成的离子液体固定相具有较强的极性,其保留性能不仅与阳离子取代基的性质密切相关,而且受取代基结构和阴离子影响明显;在考察的温度范围内,测试化合物的保留指数变化规律与传统色谱固定相完全相同。     

喹喔啉氮氧自由基-Zn(Ⅱ)配合物的合成、结构和磁性质

采用喹喔啉基取代的氮氧自由基NITQ与锌(Ⅱ)离子进行配位,得到了1个单核的双自旋配合物[Zn(acac)₂(NITQ)₂]·2CH₂Cl₂(其中acac=乙酰丙酮阴离子,NITQ=2-(2'-喹喔啉基)-4,4,5,5-四甲基咪唑啉-3-氧化-1-氧基自由基)。 X射线单晶衍射分析结果表明,两个NITQ自由基作为单齿配体分别与Zn(acac)₂配位,形成八面体构型的双自旋配合物。 变温磁化率研究表明,NITQ自由基间存在铁磁相互作用,其居里常数C=0.7242 cm³·K/mol,外斯常数θ=0.5958 K。     

硅烷基咪唑双三氟甲烷磺酰亚胺离子液体气相色谱固定相的性能评价

以双三氟甲烷磺酰亚胺离子([NTf₂]^-)为阴离子,合成阳离子烷基取代不同(C1、C2和C4)的硅烷基咪唑离子液体,以其为固定相制备气相色谱填充柱。 硅烷基咪唑离子液体为强极性固定相;阳离子结构影响固定相的热稳定性、极性和分离性能。 在这些离子液体固定相中,1-丁基-3-[(3-三甲氧基硅基)-丙基]咪唑双三氟甲烷磺酰亚胺([PBIM]NTf₂)对Grob试剂分离性能较好。 利用溶剂化作用参数模型,评价[PBIM]NTf₂固定相特性,研究固定相-组分分子之间相互作用机制;同时考察[PBIM]NTf₂色谱柱对不同类型化合物的分离性能。 结果表明,[PBIM]NTf₂固定相主要作用力是氢键碱性和偶极作用,对烷烃、醇、酯和胺等不同类型的样品组分表现出良好的分离能力。     

咪唑类离子液体混合物吸收CO2性能研究

结合常规离子液体和功能型离子液体在吸收CO₂方面的优势,将两类咪唑类离子液体进行混合,对其吸收CO₂的效果和再生性能进行了实验研究。结果表明,两类咪唑类离子液体混合后流动性明显改善,与CO₂接触气液传质顺畅;常规离子液体[bmim][BF₄]和[bmim][Tf₂N]与胺功能型离子液体[NH₂e-mim][BF₄]混合物较单一的离子液体吸收CO₂的量大,[bmim][CH₃CO₂]与[NH₂e-mim][BF₄]混合后较单一的[bmim][CH₃CO₂]吸收量有明显的减低;随着常规咪唑类离子液体阳离子碳链增长,混合离子液体吸收CO₂的效果变强;与胺乙基功能型离子液体混合吸收CO₂时,阴离子为[Tf₂N]的常规咪唑类离子液体要比阴离子为[BF₄]的吸收效果好;离子液体混合物吸收CO₂后经再生循环利用10次,混合物质量基本不变,循环使用后吸收CO₂性能为初始吸收性能的75%~85%。     

功能化酸性离子液体脱除模拟油品中的非碱性氮

合成了一系列功能化酸性离子液体并用于模拟油品中非碱性氮-吲哚的脱除。结果表明,离子液体的阴离子对脱氮率有较大影响,离子液体的酸性越强,对吲哚的选择性脱除效果越好,不同阴离子的脱氮率顺序为：HSO₄^- > CF₃COO^- > H₂PO₄^- > CH₃COO^-。以（CH₃CH₂）₃N（CH₂）₃SO₃HHSO₄为例,考察了剂油比、剂水比、沉降时间、反应时间和温度对油品脱氮率的影响。结果表明,在优化的工艺路线下,（CH₃CH₂）₃N（CH₂）₃SO₃HHSO₄对油品中的吲哚脱除率可达99.12%,重复使用六次后,脱氮活性未见明显降低,具有良好的稳定性,。     

辅酶B12模型化合物的研究(Ⅵ)──轴向及平面配体对RCo(salen)L和RCo(SB)L中Co─C键稳定性的影响

合成与表征了两类14种烷基钴Schiff碱配合物RCo(chel)L(R=CH₃,C₂H₅,n-C₃H₇,n-C₄H₉,i-C₄H₉;chel=salen,SB;L=Py,γ-pic,PPh₃),其中RCo(SB)L是一类新的辅酶B₁₂模型化合物,五配位的C₂H₅Co(SB)也是首次报道。研究了在固态和溶液中配合物的性质,并讨论了影响配合物中Co─C键稳定性的因素。     

氮杂冠醚化双Schiff碱配合物催化羧酸酯水解的研究

将4种氮杂冠醚取代的双Schiff碱钴(H)、锰(m)配合物作为仿水解酶模型催化羧酸酯(PNPP)水解.考察了Schiff碱配合物中氮杂冠醚取代的位置、氮杂冠醚的数目对其仿水解酶性能的影响;探讨了Schiff配合物催化PNPP水解的动力学和机理;提出了配合物催化PNPP水解的动力学模型.结果表明,在25℃条件下随着缓冲溶液pH值的增大,配合物催化PNPP水解速率提高;四种氮杂冠醚取代的双Schiff碱配合物在催化PNPP水解反应中表现出良好的催化活性;氮杂冠醚3-取代的Schiff碱配合物CoL2的催化活性高于5-取代的Schiff碱配合物CoL1,含有2个氮杂冠醚的配合物CoL3的催化活性高于含有1个氮杂冠醚的配合物CoL2.     

UiO-66-NH2接枝吡啶亚胺钴系催化剂的合成及催化乙烯齐聚性能

以金属有机骨架(MOFs)UiO-66-NH2和吡啶-2-甲醛为原料,采用后合成修饰法制备一种UiO-66-NH2接枝吡啶亚胺配体,然后以UiO-66-NH2接枝吡啶亚胺配体和CoCl2·6H2O为原料,经配合反应,合成出一种UiO-66-NH2接枝吡啶亚胺钴系催化剂.采用傅里叶红外变换光谱(FT-IR)、X射线衍射(...     

Syntheses and Biological Activities of Novel 3-Bromo-1-（3-chloropy- ridin-2-yl）-N-hydroxy-N-aryl- 1H-pyrazole-5-carboxamides

A series of novel 3-bromo-1-（3-chloropyridin-2-yl）-N-hydroxy-N-aryl-lH-pyrazole-5-carboxamides was synthesized by the reaction of pyrazole carbonyl chloride with each of substituted phenylhydroxyamines. The latter ones were prepared in good yields by reducing substituted nitrobenzene compounds with Zn/NH4CI reductant system in alcohol. Structures of the title compounds were determined by IR, 1H NMR, and HRMS. Their insecticidal and fungicidal activities were evaluated by larvicidal test against oriental armyworm and the mycelium growth rate method, respectively.     

A simple and efficient procedure for the synthesis of optically active s-triazolothiadiazole derivatives

A series of novel s-triazolothiadiazoles 3a-h were prepared by condensation reaction of substituted amino triazoles la-b with N-phethaloyl-L-amino acids 2a-d in the presence of the phosphoroxy chloride（POCl₃） as an anhydrous reagent.The structure of all synthesized compounds was confirmed by IR,¹H NMR,and ¹³C NMR spectroscopy.     

钯-高分子载体催化剂对糠醛加氢液相反应的研究

以弱碱性苯乙烯系阴离子交换树脂[D392,-NH₂,D382,-NHCH₃,D301R,-NH(CH₃)₂],强碱性苯乙烯系阴离子交换树脂[201×7DVB,-NH⁺(CH₃)₃]和弱碱性环氧系阴离子交换树脂(701,-NH₂)为载体制备了3种钯-高分子载体催化剂.考察了反应条件、高分子载体的种类、钯含量和催化剂用量对糠醛催化加氢生成四氢糠醇反应及催化性能的影响.在体积分数为50%的乙醇-水溶液和水中对糠醛常压液相加氢反应,钯-高分子载体(阴离子交换树脂D392,-NH₂,D382,-NHCH₃)催化剂均可使糠醛的加氢反应转化率达100%,生成四氢糠醇的选择性达98%以上,而用金属钯为催化剂的转化率达70%以上,选择性达97%以上.同时用XPS分析了高分子载体催化剂的结构与催化加氢反应性能的关系.     

Synthesis and Characterization of [Cu(N-MeIm)4(BF4)2] in Ionic Liquid

A new transition metal complex, [Cu(N-MeIm)₄(BF₄)₂](N-MeIm=N-methylated imidazoles, BF₄= tetrafluoroborate), was synthesized via the solvothermal method in ionic liquid. The ionic liquid acts as thermal decomposition reaction medium, soft temple agent and ligand compound. The central Cu(II) ion is coordinated by four N atoms from four N-methylated imidazole ligands, and the four N-methylated imidazole rings are perpendicular to each other. The crystal structure of [Cu(N-MeIm)₄(BF₄)₂] was determined by single crystal X-ray diffraction. The results of thermogravimetry(TG) and Fourier transform infrared spectrometry(FTIR) analyses were in accordance with that of crystal structure. The complex showed strong ligand-based absorbance with maximum wavelength at 208 and 231 nm, which are attributed to π-π^* transition of the N-methylated imidazole ligands.     

Studies on Nucleophilic Ring-Opning Reaction of Ethylene Epoxide by (μ- CH3S)(μ-IMIgS) Fe2 (CO)6——Syntheais and Crystal Structure of (μ-Methylthio)- (μ- R -Hydroxylethylthio)hexacarbonyldiiron

A new type of Fe-S complex (C), (μ -CH₃S) (μ-HOCH₂CH₂S) Fe₂(CO)₆ which contains μ-β-hydroxyethyl, has been synthesized in high yield through ring-opening reaction of ethylene epoxide under uncleophilic attack of active complex (A), (μ-CH₃S)(μ-IMgS) Fe₂(CO)₆, followed byan alcoholysis of the intermediate (B). The crystal structure of (C) was determined by an X-ray diffraction technique. The crystal belongs to monoclinic system with space group of C₂/c. Cell parameters a= 15.784(3), b = 22.172(3), c=9.774(2)Å, β=119.53(2)°, V=2976.3ų. D_c = 1.80g cm^-3, Z=8, F(000)=1616 and final R=0.077.     

Zr-TUD-1: A novel heterogeneous catalyst for the Meerwein–Ponndorf–Verley reaction

A series of Schiff-base complexes has been synthesized by the condensation of 1,2-diaminocyclohexane with salicylaldehyde, 2-pyridinecarboxaldehyde, and 2-hydroxy-1-naphthaldehyde, followed by the metallation with manganese (1, 2, 3a), cobalt (3b), copper (3c) and iron (3d) salts. These Schiff-base ligands L₁–L₃ and complexes 1, 2, 3a–d were then characterized by IR, ¹H NMR, ¹³C NMR, UV–vis spectra, and DSC measurement. Schiff-base Mn complex (3a) resulting from N,N′-bis(2-hydroxy-1-naphthalidene)cyclohexanediamine (L₃) ligand was considerably active for the catalytic epoxidation of styrene under mild conditions, in which the highest yield of styrene oxide reached 91.2 mol%, notably higher than those achieved from simple salt catalysts Mn(Ac)₂·4H₂O and MnSO₄·H₂O. However, another two salen–Mn complexes 1 and 2 derived from ligands N,N′-bis(salicylidene)cyclohexanediamine (L₁) and N,N′-bis(2-pyridine carboxalidene)cyclohexanediamine (L₂) exhibited relatively poor activity under identical experimental conditions.     

顺二氨二水合铂(Ⅱ)与生物膜磷脂反应的核磁共振研究

用NMR法研究了顺二氨二水合铂(Ⅱ)(AAP)与α-二棕搁酸磷脂酰胆碱(DPPC)的相互作用方式,以阐明在顺铂-细胞相互作用中膜磷脂的贡献。¹H及¹³C谱表明,DPPC与AAP在CDCl₃中作用时,铂结合在DPPC的头部并引起DPPC分子中gauche向trans的构象转变。65℃测定DPPC脂质体与AAP在D₂O溶液中反应不同时间后的-N(CH₃)₃、-(CH₂)_n及-CH₃基团¹H的T₁值表明,铂在磷脂上的结合引起的磷脂构象变化会导致膜分子重新装配。     

超支化分子桥联水杨醛亚胺镍配合物的合成及对乙烯齐聚反应的催化性能

合成了一种具有超支化结构的新型水杨醛亚胺配体及其Ni(Ⅱ)配合物, 利用元素分析、 电喷雾电离质谱(ESI-MS)、 傅里叶变换红外光谱(FTIR)、 紫外-可见光谱(UV-Vis)、 氢核磁共振谱(¹H NMR)和碳核磁共振谱(¹³C NMR)对其结构进行了表征. 以甲基铝氧烷(MAO)为助催化剂, 考察了超支化水杨醛亚胺镍配合物对乙烯齐聚反应的催化活性及聚合条件(Al/Ni摩尔比、 聚合温度)对催化剂活性及聚合产物分布的影响. 结果表明, 在反应温度为25 ℃、 Al/Ni摩尔比为500时, 该催化剂的活性最高达到5.59×10⁵ g/(mol Ni·h), 得到的聚合产物为全馏分烯烃, 其中高碳烯烃C₁₀~C₁₈的含量最高达91%.     

The exploration of chiral N-cyano sulfiliminyl dicarboxamides on insecticidal activities

Due to new mechanism of action and ecofriendly characteristics,dicarboxamide insecticides have attracted more and more attentions in modern pest management.A series of 20 dual chiral N-cyano sulfilimines containing two centers(carbon and sulfur) were designed and synthesized.All title compounds were determined by ~1H NMR,high-resolution mass spectrometry(HRMS) and optical polarimeter.The preliminary results indicated that some of them exhibited favourable insecticidal activities against oriental armyworm(Pseudaletia separata Walker).These isomers exhibited different impact on activity following the sequence as(Sc,Ss) (Sc,Rs),and the rule of title compounds' activity against oriental armyworm was 3-CF_3≥2—CH_3—4—Cl2,3,4-trifluro in the anilide moiety.The results indicated that these groups such as 3-CF_3,2—CH_3—4—Cl or 2,3,4-trifluro were inefficient to replace heptafluoroisopropyl group for high larvicidal activity,which provided some guidance for the further modifications of sulfiliminyl dicarboxamides.