Ionic iron（III） complex of aryloxo-linked bis（imidazolium） cations： efficient and recyclable catalyst for aryl Grignard cross-coupling of alkyl chlorides

A novel phenol-linked bis（imidazolium） salt, H3LCl2 （L = O-4-C（CH3）3-C6H2-2,6-di[CH2{C（NCHCH- NAr）}]2, Ar = 2,6-diisopropylphenyl, 1）, was designed and used to prepare an ionic iron（III） complex [H2L][FeCl4] （2）. Complex 2 was a highly efficient catalyst for aryl Grignard cross-coupling of alkyl chlorides bearing β-hydrogens. Furthermore, complex 2 was reusable and could be reused in at least eight times without significant loss in catalytic activity.     

Development of Fe(III)-containing ether-functionalized imidazolium ionic liquids for aryl Grignard cross-coupling of alkyl halides

A series of Fe(Ⅲ)-containing imidazolium-based ionic liquids containing ether substituents,including[C3OMim][FeCl4](1,[C3OMim]=1-(2-methoxyethyl)-3-methylimidazolium),[C3OiPim][FeCl4](2,[C3OiPim]=1-isopropyl-3-(2-methoxyethyl)imidazolium),[C3OBim][FeCl4](3,[C3OBim]=1-butyl-3-(2-methoxyethyl)imidazolium),[(C3O)2im][FeCl4](4,[(C3O)2im]=1,3-bis(2-methoxyethyl)imidazolium),[C3OMim][FeBr4](5)and[(C3O)2im][FeBr4](6),were prepared and characterized by elemental analysis,Raman spectroscopy and electrospray ionization mass spectrometry.The catalytic performances of 1–6 and related Fe(III)-based catalysts in the cross-coupling of aryl Grignard reagents with alkyl halides bearing-hydrogens were studied,revealing that mono(ether)functionality improves the catalytic activity and that bis(ether)functionality improves the reusability.After simply decanting the product contained in the ethereal layer,complex 4,which containing bis(ether)-functionalized imidazolium cation,could be successfully recycled seven times.     

离子液体在水、乙醇及其混合物中的电导率测定

用电导率仪测定了298.15 K条件下多种离子液体,即1-甲基-3-乙基咪唑溴([Emim]Br)、1-甲基-3-丁基咪唑溴([Bmim]Br)、1-甲基-3-丁基咪唑氯([Bmim]Cl)、1-甲基-3-丁基咪唑氟硼酸盐([Bmim][BF4])、1-甲基-3-甲基咪唑磷酸二甲酯([Mmim][DMP])、1-甲基-3-乙基咪唑磷酸二乙酯([Emim][DEP])、1-甲基-3-丁基咪唑磷酸二丁酯([Bmim][DBP])以及醋酸钾(KAc)在水、乙醇及其混合溶剂中的电导率数据。结果表明,室温离子液体的电导率顺序为：[Bmim][BF4]>[Mmim][DMP]> [Emim][DEP]> [Bmim][DBP],该顺序与离子液体的黏度成反比。离子液体在水中的电导率的次序大致为[Emim]Br>[Bmim]Cl[Bmim]Br[Bmim][BF4]>[Mmim][DMP]>[Emim][DEP]> [Bmim][DBP]。离子液体在水中的电导率高于在乙醇中的电导率,且电导率随浓度的增加均先升高后降低。与醋酸钾相比,溶剂变化对离子液体电导率的影响要小得多。离子液体[Mmim][DMP]和[Emim][DEP]能显著提高乙醇水溶液中乙醇的相对挥发度,且盐析作用[Mmim][DMP]> [Emim][DEP],这与在混合溶剂中电导率的大小次序是一致的。     

离子液体萃取锝和铼的研究

系统地研究离子液体对ReO_4~-和TcO_4~-的萃取。结果发现,咪唑类和季铵盐类离子液体可通过阴离子交换机理高效萃取ReO_4~-和TcO_4~-。其中,PF_6~-类离子液体对ReO_4~-和TcO_4~-的萃取效率明显高于NTf_2~-类离子液体。当阴离子相同时,离子液体阳离子侧链增长,萃取效率增大。增加水相HNO_3浓度或在水相中加入相应离子液体的阴离子可以抑制ReO_4~-和TcO_4~-的萃取。水相中加入相应离子液体的阳离子则可以促进萃取反应进行。在低酸度下,己基三丁基铵双三氟甲烷磺酰亚胺[N_(6,444)][NTf2]和1-辛基-3-甲基咪唑六氟磷酸盐[C_8mim][PF_6]对模拟废液中的ReO_4~-均具有很好的萃取选择性。LiNTf_2和KPF_6水溶液可以分别实现对[N_(6,444)][NTf_2]和[C_8mim][PF6]中ReO_4~-的有效反萃。     

Decompression-induced disorder to order phase transition in low-melting ionic liquid [OMIM][PF6]

In situ pressure-induced Raman spectral changes of 1-octyl-3-methyl imidazolium hexafluorophosphate （[OMIM][PF6]） have been investigated under the pressure up to 5.86 GPa at room temperature. The results indicated that [OMIM][PF6] experienced a phase transition at about 4.12 GPa during compression, and it was thought as a phase transition of liquid to a superpressurized glass. Upon decompression, from the obvious change of Raman spectra of [OMIM][PF6] at about 0.48 GPa, it could be inferred that a decompression-induced disorder to order phase transition in [OMIM][PF6] occurred. The phase behavior of [OMIM] [PF6] at low temperature under atmospheric pressure was also investigated in detail. The result showed that Raman spectra of [OMIM][PF6] varied slightly and no crystallization occurred upon cooling. These facts suggested that a disorder to order phase transition was induced by decompression in [OMIM][PF6], and [OMIM][PF6] served as a superpressurized glass under the pressure above 4.12 GPa, which was similar to the glassy state at low temperature.     

反式[FeCl2(H2O)"4]+加合瓜环的超分子结构

作为[FeCl2(H2O)4]Cl·(C36H36N24012)·4H2O加合物的一部分,反式[FeCl2(H2O)4]+的结构首次被单晶X-射线衍射分析方法加以证实.同时还用该方法解析了[FeCl2(H2O)4]Cl·(C36H36N24012)·4H2O加合物的晶体结构.     

Synthesis, structure of iron(III)-containing imidazolium salts and their catalytic activity in the alkylation of aryl Grignard reagents

A series of iron(III)-containing imidazolium salts of the general formula [DRim][FeX₄] (R = 2,6-diisopropylphenyl, IPr, X = Cl, 1; R = IPr, X = Br, 2; R = tertbutyl, ^t Bu, X = Cl, 3; R = isopropyl, ⁱ Pr, X = Cl, 4; R = benzyl, Bn, X = Cl, 5; R = Bn, X = Br, 6) have been prepared in high yields via reactions of anhydrous ferric halides with equivalent of the corresponding N,N-dihydrocarby-limidazolium halides, where 2–6 are novel ones. All of the complexes were characterized by elemental analysis, Raman spectroscopy, electrospray ionization mass spectroscopy, and X-ray crystallography for 1 and 2. All of them were non-hygroscopic and air-stable, with four of them existing as solids (1–4) and two as liquids (5 and 6) at room temperature. A preliminary catalytic study on the coupling of 4-tolylmagnesium bromide with cyclohexyl bromide revealed that 1 and 3 possessed the highest activity. In comparison, 2, 4 and 5 exhibited moderate activity and the least active complex was 6.     

A new synthetic approach to the ferritin core uncovers the soluble iron(III) oxo-hydroxo aggregate [Fe11O6(OH)6(O2CPh)15]

Hydrolytic polymerization of iron(III) occurs in many reactions in vivo, for example, the formation of bacterial magnetite in magnetotactic organisms, biomineralization of iron and the synthesis of the metallic core of the iron-storage protein ferritin. The ferritin core contains aggregates of up to 4,500 oxygen-bridged, octahedrally coordinated, high-spin iron(III) centres and is attached to the protein shell through carboxylate groups of amino-acid side chains. The X-ray and electron-diffraction patterns of this core resemble those of the mineral ferrihydrite, a hydrated iron oxide formed in nature, inter alia, by iron-dependent bacteria. The preparation and structural characterization of such large poly-iron aggregates has been a challenge to inorganic chemists. We have recently shown that tri- and tetranuclear iron(III) oxo complexes of the type thought to be important in ferritin-core formation can be prepared by reacting mononuclear [FeCl4]- and binuclear [Fe2OCl6]2- components in aprotic solvents (ref. 9 and S.M.G., W. H. Armstrong and S.J.L., in preparation). Here we report the discovery of a remarkable new molecule, [Fe11O6(OH)6(O2CPh)15], obtained by hydrolysis of the [Fe2O]4+ unit in the presence of limited amounts of water and carboxylate salts. The synthesis and properties of this soluble iron(III) oxohydroxo aggregate should help to elucidate the mechanism of formation of poly-iron centres.     

取代酚-咪唑 型环番的合成

用２，６－二（咪唑甲基）－４－氯苯酚分别与邻、间、对－二（溴甲基）苯或２，６－二（溴甲基）吡啶反应，合成了一类新型的取代酚－咪唑钅翁型环番．所有化合物均被ＭＳ，１ＨＮＭＲ，ＩＲ和元素分析证实     

咪唑基离子液体与小分子相互作用的理论研究

采用密度泛函理论考察了1-乙基-3-甲基咪唑四氟合硼酸盐（[EMIM][BF4]）和2-甲基噻吩（2-MT）、正己烷（HEX）、异丁基硫醇（IBT）的相互作用。采用GGA/PW91和DNP基组优化了结构,并用NBO和AIM分析了[EMIM][BF4]和2-甲基噻吩（2-MT）、正己烷（HEX）、异丁基硫醇（IBT）的氢键相互作用。[EMIM][BF4]离子对最稳定的气相结构表明,[BF4]-阴离子的F原子和咪唑环上C2-H2的氢键作用在形成离子对中起重要作用。[BF4]-阴离子和[EMIM]＋阳离子支链发生氢键作用。[BF4]-阴离子趋向于C2-H2形成氢键,这说明,2-甲基噻吩（2-MT）、正己烷（HEX）、异丁基硫醇（IBT）吸附在[EMIM][BF4]上没有改变离子液体离子对的主要作用。[EMIM][BF4]和2-甲基噻吩发生π···C-H和氢键作用,而[EMIM][BF4]和正己烷（HEX）、异丁基硫醇（IBT）主要发生氢键作用。相互作用能表明,2-甲基噻吩优先吸附在离子液体上。     

烷基咪唑氟硼酸盐离子液体的合成与溶剂性质研究

研究了反应温度、时间和溶剂等对烷基咪唑氟硼酸盐室温离子液体[R1R2Im]BF4产率的影响,考察了该离子液体溶剂的性质。结果表明,[R1R2Im]BF4与油品中的脂肪族烃类组分不能互溶,但对部分含硫含氮组分均有一定的溶解度,同时还能溶解具有Lewis酸性的AlCl3和杂多酸络合物以及具有加氢活性的无机盐,这为开发Lewis酸催化或加氢催化等离子液体油品液/液双相催化体系奠定了基础。运用量子化学计算方法,考察了[R1R2Im]BF4的电导率与离子液体的分子结构的内在联系。结果表明,当阴离子相同时,N 烷基咪唑阳离子的体积越大,对应的离子液体的电导率越小。     

氯化1-甲基-3-丁基咪唑盐的合成、表征及脱硫研究

N-甲基咪唑与氯代正丁烷亲核取代生成产物氯化1-甲基-3-丁基咪唑盐([BMIM]Cl),其分子结构经FT-IR、13C-NMR、UV、MS等表征手段得以确认.用单因素分析法考察了萃取时间、萃取温度、含硫化合物种类、剂油体积比对萃取脱硫效果的影响.结果表明,在剂油比为1∶1,萃取时间为30 min,萃取温度为40℃的温和反应条件下二苯并噻吩(DBT)的单级萃取脱除率为56.2%.多级萃取和萃取-氧化耦合脱硫操作研究表明:在最优单级萃取条件下,DBT经四级连续萃取脱除率可达97.6%;萃取-氧化耦合脱硫体系对3种含硫物质均能实现85%以上的脱除.     

Ionic liquids containing the urea moiety for recognition of halides and complex anions

A series of novel imidazolium based ionic liquids containing the urea moiety were designed and synthesized for anion recognition. 1-Ethylurea-3-methylimidazolium acetate ([Eumim]OAc) was used as the receptor for the halides and complex anions (BF4-, PF6-, BPh4-). 1H NMR spectra showed that the urea protons and imidazolium C(2) proton of the receptor ([Eumim]OAc) moved upfield on addition of various anions. A Job plot showed that the [Eumim]OAc receptor formed a 1:1 complex with BPh4-. X-ray diffraction analysis and the molecular modeling study revealed that the conformations of [Eumim]OAc and [Eumim]BPh4 were different. The conformational change of the cation was caused by anion exchange, and may provide an alternative to current methods for recognition of anions.     

Synthesis and characterization of novel bridged porphyrins

The reaction of 5-(4-hydroxyphenyl)-10,15,20-triphenyl porphyrin with 2,6-dibromomethylpyridine and 4,4‘-dicarboxyl-2,2‘-bipyridine respectively gave 2,6-bis-[5,10,15-triphenyl-20-( 4-phenoxymethyl )-porphyrin-yl]-pyridine(3) and 4, 4‘-di-[5,10,15-triphenyl-20-( p-phenoxycarbonyl)-porphyrin-yl]-2,2‘-bipyridine (4). 5-[4-(4‘- Bromobutoxy) phenyl]-10, 15, 20-triphenyl porphyrin reacted with 2,6-dihydroxymethyl pyridine to give 2,6-bis-[5,10,15-triphenyl- 20-(4-(p-phenoxy)-butoxymethyl)-porphyrin-yl]-pyridine(5). Those new compounds have been identified by ^1H NMR, IR, MS and UV-visible spectra, and elemental analysis.     

Property variation of ionic liquid [Bmim][AuCl4] immobilized on carboxylated polystyrene submicrospheres with a small surface area

In order to understand the effect of surface chemical groups on the immobilized species, Au-containing imidazolium-based ionic liquid (IL) [Bmim][AuCl4] was intentionally immobilized on polystyrene (PS) submicrospheres (d～300 nm) with a very small surface area (4-10 m2/g), which possess carboxyl-moiety (COONa or COOH) on the surface. The behavior of immobilized [Bmim][AuCl4 ] on the two types of submicrospheres was investigated by transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and powder X-ray diffraction (XRD). It was revealed that the melting points (Tm) of [Bmim][AuCl4 ] that had been immobilized on PS-COONa and PS-COOH submicrospheres were decreased by 2.7 and 4.1℃, respectively. The interaction mechanism between the IL and submicrosphere surface moieties was further analyzed by X-ray absorption fine structure (XAFS) analysis. The data indicated that the coordination environment of Au species changed markedly when [Bmim] [AuCl4] was immobilized on the surfaces of PS-COONa and PS-COOH submicrospheres, as illustrated by the decrease in white line peak intensity. The effect of surface COOH groups on Tm depression and the white line peak intensity of the XANES spectrum is more pronounced than that of COONa groups, most likely due to the possible hydrogen bond formation between the COOH group and [Bmim]+.     

甲醇-甲乙酮-1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐物系等压汽液相平衡数据的测定及分析

考察了离子液体1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐（[EMIM][NTf₂]）对甲醇-甲乙酮共沸物系等压汽液相平衡的影响。首先测得了101.3 kPa下甲醇-甲乙酮-[EMIM][NTf₂]三元体系的等压汽液相平衡数据,然后用非随机双液（NRTL）模型进行了关联,平均相对偏差为1.39%,表明了NRTL模型对含离子液体三元体系的良好适用性。经NRTL模型计算,在[EMIM][NTf₂]的摩尔分数为0.047时可消除甲醇-甲乙酮共沸点。实验结果表明：[EMIM][NTf₂]的加入对甲醇-甲乙酮体系表现出极强的盐效应,改变了体系的汽液相平衡,提高了甲醇对甲乙酮相对挥发度。因此[EMIM][NTf₂]可作为甲醇-甲乙酮萃取精馏的萃取剂。     

功能性离子液体[A336][Cyanex272]对钨钼的萃取分离研究

Functionalized ionic liquids (FILs) as extractants were employed for the separation of tungsten and molybdenum from a sulfate solution for the first time. The effects of initial pH, extractant concentration, metal concentrations in the feed were comprehensively investigated. The results showed that tricaprylmethylammonium bis(2,4,4-trimethylpentyl)phosphinate ([A336][Cyanex272]) could selectively extract W over Mo at an initial pH value of 5.5; the best separation factor β_W/Mo of 25.61 was obtained for a solution with low metal concentrations (WO₃: 2.49 g/L, Mo: 1.04 g/L). The [A336][Cyanex272] system performed effectively for solutions of different W/Mo molar ratios and different metal ion concentrations in the feed. The chemical reaction between [A336][Cyanex272] and W followed the ion association mechanism, which was further proved by the Fourier-transform infrared (FTIR) spectra of loaded [A336][Cyanex272] and the free extractant. The stripping experiments indicated that 95.48% W and 100.00% Mo were stripped using a 0.20 mol/L sodium hydroxide solution. Finally, the selective extractions of W and Mo from two synthetic solutions of different high metal concentrations were obtained; the separation factor β_W/Mo reached 23.24 and 17.59 for the first and second solutions, respectively. The results suggest the feasibility of [A336][Cyanex272] as an extractant for the separation of tungsten and molybdenum.     

氯化1-辛基-3-甲基咪唑对EMT6细胞的毒性及其DNA损伤作用

研究了氯化1-辛基-3-甲基咪唑([C8mim][Cl])对EMT6细胞的毒性大小及其可能的遗传机制.不同浓度(0.06、0.25、1.00mmol·L-1)的[C8mim][Cl]对EMT6细胞染毒12h,WST-1比色法检测了细胞活力,ELISA方法检测了Bcl-2蛋白的表达,Hoechst 33342染色检测了细胞核形态的变化,单细胞凝胶电泳(SCGE)检测了细胞DNA的损伤,流式细胞仪检测了细胞周期和细胞DNA的含量.结果显示,经[C8mim][Cl]染毒后,EMT6细胞活力下降,并且呈剂量依赖关系.当[C8mim][Cl]浓度高于0.25mmol·L-1时,与对照相比,差异显著.[C8mim][Cl]染毒使Bcl-2蛋白表达下调,引起了细胞核形态改变,造成了DNA的断裂损伤和含量下降,诱导了细胞凋亡.从而可以得出结论,DNA损伤参与了[C8mim][Cl]诱导的细胞凋亡.     

三种多金属氧酸盐的制备及催化H2 O2氧化淀粉性能比较

以磷钼钒多阴离子[ PMo11 VO40]^4-、[ PMo10 V2 O40]^5-、[ PMo9 V3 O40]^6-为构建基元,分别和1-辛基-3-甲基咪唑阳离子通过离子交换反应制备三种多金属氧酸盐。以这三种多金属氧酸盐为氧化性催化剂,可溶性淀粉为原料,双氧水为氧化剂,应用于淀粉氧化实验并比较它们的催化氧化活性。试验结果显示,三种催化剂均具有较好的催化性能,其中用[Omim]4H[PMo10V2O40]（OP-MoV2）作催化剂时氧化淀粉中的羧基含量最高。     

不同烃链长度咪唑类离子液体对日本三角涡虫的急性毒性

采用SPSS软件概率单位法研究了4种不同烃链长度的咪唑类离子液体对日本三角涡虫的急性毒性.结果表明:[C4mim]Br,[C6mim]Br,[C8mim]Br和[C10mim]Br对日本三角涡虫72h、96h的半数致死浓度(LC50)分别为2 079.46和1 744.38mg·L-1,919.35和725.00mg·L-1,312.79和238.50mg·L-1以及32.57和23.25mg·L-1.由LC50值的大小可知,4种不同烃链长度的咪唑类离子液体的毒性[C10mim]Br>[C8mim]Br>[C6mim]Br>[C4mim]Br.由此可见,咪唑类离子液体对涡虫的急性毒性大小与其烷基侧链长度密切相关,碳链越长毒性越大.此外,根据急性毒性试验涡虫的中毒症状,也就离子液体对涡虫可能的靶器官问题进行了初步探讨.