咪唑离子液体催化下胺对α,β-不饱和酰胺的迈克尔加成反应

咪唑类离子液体作为可循环使用的绿色催化剂,近几年广泛应用于有机合成反应中.研究了4种1-丁基-3-甲基咪唑类离子液体在无溶剂室温条件下对胺和不饱和酰胺的迈克尔加成反应,发现[Bmim][NH_2CH_2COO]离子液体显现出较高的催化活性,当加入15%的催化剂反应3h均能得到较高的产率.此外,所用催化剂能够循环利用并能大规模生产.     

酸性咪唑类离子液体催化合成2-氯丙酸乙酯

研究了酸性咪唑类离子液体中2-氯丙酸乙醇的合成.制备了4种咪唑类离子液体作为催化剂用于酯化反应,通过Hammett方法测定其酸度,讨论了酸度-催化活性之间的关系.实验发现[Hmim] HSO4拥有比其它几种离子液体更好的催化效果.考察了离子液体用量、反应物配比、反应时间和反应温度对反应结果的影响.得到较佳的反应条件:n...     

咪唑类离子液体的研究进展

咪唑类离子液体以其独特的物理化学性质和在众多领域的巨大应用潜能而引起广泛的关注.本文结合我们的研究工作,对近期国际上关于咪唑类离子液体的气-液和液-液平衡、咪唑类离子液体的表面活性剂行为、传统表面活性剂在咪唑类离子液体中聚集体的形成、表面活性剂/水(油)/咪唑类离子液体三元体系超分子自组装体形成等方面的一些主要研究成果进行了综合评述.在此基础上,提出了进一步开展非传统表面活性剂/离子液体体系超分子自组装体及离子液体结构对聚集体形成、结构、性质影响等研究的设想.     

石英晶体微天平技术研究咪唑类离子液体与气体分子的相互作用

基于石英晶体微天平(Quartz Crystal Microbalance, QCM)技术, 建立了一种测定气体在离子液体(ILs)中基本热力学参数的方法. 测定了5种可挥发有机物(VOCs)在6种咪唑类离子液体中的亨利常数, 并对可能的作用机理进行了探讨. 结果表明, QCM技术可以作为研究离子液体溶解性和作用规律的有效方法.     

咪唑类含能离子液体的合成及性能研究

以N-甲基咪唑、1,2-二甲基咪唑和2-氯乙醇为原料,经季铵化、硝化和复分解反应,合成了一系列咪唑类含能离子液体.通过紫外可见光谱、红外光谱、质谱、核磁共振和元素分析等对结构进行了表征.研究了其在常用有机溶剂中的溶解性,结果表明所合成的咪唑类含能离子液体在极性溶剂中具有良好的溶解性.采用热重分析法和差示扫描量热法研究了其热性能,结果表明所合成的含能离子液体具有良好的热稳定性,其中N-硝酰氧乙基咪唑硝酸盐的分解温度均在160℃左右,而N-羟乙基咪唑离子盐的分解温度均超过了190℃.差示扫描量热技术(DSC)实验表明,1-(2-硝酰氧乙基)-3-甲基咪唑硝酸盐和N-羟乙基咪唑类离子盐在二次升温过程中均发生了玻璃化转变,表现出了离子液体的特有性质.采用Kamlet-Jacobs方程估算了合成的含能离子液体的爆速和爆压等爆轰参数.     

咪唑类离子液体的合成及其在分析化学中的应用

本文介绍了咪唑类离子液体的合成,特别是以BF4-、PF6-为阴离子的咪唑类离子液体的合成,并重点综述了近年来咪唑类离子液体在电化学分析、质谱、光谱、色谱及毛细管电泳等分析化学中的应用.     

离子液体功能化手性salen Mn(Ⅲ)配合物不对称催化仲醇氧化动力学拆分反应

采用共价键联法,将亲水性咪唑类离子液体结构引入手性salen Mn(Ⅲ)配合物的C5位,制备了离子液体功能化手性salen Mn(Ⅲ)配合物.傅里叶变换红外光谱、紫外光谱和旋光分析等结果表明,咪唑类离子液体结构已嫁接到手性salen Mn(Ⅲ)配合物结构中,且嫁接过程未破坏催化活性中心.在以PhI(OAc)2为氧化剂,H2O/CH2Cl2为溶剂的(+/-)-α-甲基苯甲醇不对称氧化动力学拆分反应中,该催化剂表现出比传统手性salen Mn(Ⅲ)催化剂更高的催化活性,仲醇的转化率达到63%以上,对映选择性为99%,拆分效率为18.3%.可通过调变溶剂实现催化剂的分离并重复使用3次以上.实验结果表明,亲水性咪唑离子液体可改善水相反应传质问题且有利于稳定催化活性中间体,从而提高催化活性及稳定性.     

1,3-二取代咪唑类离子液体熔点预测

以16种咪唑类四氟硼酸盐和22种咪唑类六氟磷酸盐为研究对象, 采用QSAR(quantitative structure-activity relationship)方法和遗传算法对其熔点与结构的定量构效关系进行了研究, 以实现对两类咪唑类离子液体熔点的预测. 建立的咪唑类四氟硼酸盐三参数模型相关系数R2为0.89, 咪唑类六氟磷酸盐四参数模型相关系数R2为0.85; 使用留一法对两模型进行内部验证的相关系数R2分别为0.82和0.77, 两预测模型具有真实有效性; 使用测试集对两模型进行外部验证, 所得两模型的平均预测绝对误差分别为11.43和7.78 K, 优于文献报道水平, 可得出结论, 两模型均具有较好的熔点预测能力.     

新型室温离子液体六烷基胍盐的制备及性质

近年来 ,离子液体 (IL)作为“绿色”溶剂受到学术和工业界的关注 .英国 BP公司和法国的 IFP等研究机构从 2 0世纪 80年代起就开始探索离子液体作为溶剂与催化剂的可能性 ,至今在离子液体体系中已实现了许多催化反应 [1～ 5] .室温离子液体 (RTIL S)是指在常温下呈液态的熔盐体系 .通常由烷基吡啶或双烷基咪唑季铵阳离子与氯铝酸根、氟硼酸根及氟磷酸根等阴离子组成 .在季铵盐类离子液体中 ,咪唑盐的合成和应用研究尤为突出 .目前 ,对于既可作为溶剂又可作为催化剂的室温离子液体的合成和应用已成为研究热点 [6 ] ,如室温离子液体 [EMI…     

稀散金属室温离子液体研究Ⅰ.InCl3/BPC体系

利用差示扫描量热曲线(DSC)方法构筑了InCl3/BPC二元体系相图,并指出该体系可形成含稀散金属的室温离子液体,有一定宽度的室温离子液体窗口和较小的室温离子液体深度.从头算和Raman光谱都指出,在InCl3/BPC体系室温离子液体中InCl-4是主要负离子.     

Synthesis, reactivity, and structure of strictly homologous 18 and 19 valence electron iron nitrosyl complexes

The 18 and 19 valence electron (VE) nitrosyl complexes [Fe(NO)('pyS4')]BF4 ([1]BF4) and [Fe(NO)('pyS4')] (2) have been synthesized from [Fe('pyS4')]x ('pyS4'(2-) = 2,6-bis(2-mercaptophenylthiomethyl)pyridine(2-)) and either NOBF4 or NO gas. Complex [1]BF4 was also obtained from [Fe(CO)('pyS4')] and NOBF4. The cation [1]+ is reversibly reduced to give 2. Oxidation of 2 by [Cp2Fe]PF6 afforded [Fe(NO)('pyS4')]PF6 ([1]PF6). The molecular structures of [1]PF6 and 2 were determined by X-ray crystallography. They demonstrate that addition of one electron to [1]+ causes a significant elongation of the Fe-donor atom bonds and a bending of the FeNO angle. Density functional calculations show that the unpaired electron in 2 occupies an orbital, which is antibonding with respect to all Fe-ligand interactions. As expected from qualitative Molecular Orbital (MO) theory, it has a large contribution from a pi* type NO orbital. The nu(NO) frequency decreases from 1893 cm(-1) in [1]BF4 to 1648 cm(-1) in 2 (in KBr). The antibonding character of the unpaired electron explains the ready reaction of 2 with excess NO to give [Fe(NO)2('pyS4')] (3), the facile NO/CO exchange of 2 to afford [Fe(CO)('pyS4')], and the easy oxidation of 2 to [1]+.     

One-pot conditional self-assembly of multicopper metallacycles

The self-assembly of supramolecular metallacycles via the coordination-driven directional bonding approach can be modified to produce some unexpected structural variations. The combination of a flexible ligand-capped dinuclear transition-metal acceptor like [Cu(2)(dppm)(2)(NCMe)(2)]X(2) (1X(2); dppm = Ph(2)PCH(2)PPh(2); X(-) = BF(4)(-), PF(6)(-), or BPh(4)(-)) with monodentate-bidentate donors like 2-, 3-, and 4-pyridylcarboxylates produced oligomeric compounds [{Cu(2)(dppm)(2)}(μ-(2-PyCO(2)))](2)X(2) (2X(2)), [{Cu(2)(dppm)(2)}(μ-(3-PyCO(2)))](2)X(2) (3X(2)), and [{Cu(2)(dppm)(2)}(μ-(4-PyCO(2)))](4)X(4) (4X(4)), respectively, as the thermodynamically stable products in one-pot reactions. However, the modified self-assembly is still subject to steric hindrance. The reaction of complex 1(BF(4))(2) with 6-Me-3-PyCO(2)H did not produce a polygonal dimeric metallacycle but a simple dinuclear complex, [Cu(2)(dppm)(2)(6-Me-3-PyCO(2))](BF(4)) (5(BF(4))). The crystal structures of complexes 2(PF(6))(2), 3(PF(6))(2), 4(BF(4))(4), and 5(BF(4)) were determined using X-ray diffraction.     

Self-Assembly of Ribbons and Frameworks Containing Large Channels Based upon Methylene-Bridged Dithio-, Diseleno-, and Ditelluroethers

Homoleptic copper(I) and silver(I) complexes [M(n)(L-L)(2)(n)()](BF(4))(n)() (M = Cu or Ag; L-L = MeECH(2)EMe; E = S, Se or Te) have been prepared and characterized by analysis, FAB mass spectrometry, and IR and multinuclear NMR spectroscopy ((1)H, (77)Se, (125)Te, (63)Cu and (109)Ag). The single-crystal X-ray structures of [Cu(n)()(MeSeCH(2)SeMe)(2)(n)()](PF(6))(n)() (orthorhombic, P2(1)2(1)2(1), a = 10.879(7) ?, b = 16.073(7) ?, c = 9.19(1) ?, Z = 4) and [Ag(n)()(MeSeCH(2)SeMe)(2)(n)()](BF(4))(n)() (monoclinic, P2(1)/c, a = 14.546(9) ?, b = 14.65(1) ?, c = 30.203(9) ?, Z = 4) reveal extended three-dimensional cationic frameworks in the solid state which contain large cylindrical or rectangular channels accommodating the PF(6)(-) or BF(4)(-) counterions. In contrast, a single-crystal X-ray structure of [Cu(n)()(MeSCH(2)SMe)(2)(n)()](PF(6))(n)().nMeNO(2) (orthorhombic, Pbcn, a = 15.506(3) ?, b = 8.934(2) ?, c = 25.859(3) ?, Z = 8) shows tetrahedral Cu(I) ions coordinated to bridging dithioethers forming an cationic ribbon-like arrangement of 8-membered rings. Adjacent rings are linked by the Cu atoms. Variable temperature NMR studies have been used to probe various exchange processes occurring in solution in these systems.     

Topological variations of the PDP ligand and its prospects in molybdenum(0) dearomatization agents

The compounds fac-(κ(3)-PDP)Mo(CO)(3) {1; PDP = 2-[[2-(1-(pyridin-2-ylmethyl)pyrrolidin-2-yl)pyrrolidin-1-yl]methyl]pyridine}, [(cis-β-PDP)Mo(NO)(CO)]PF(6) ([cis-β-3]PF(6)), [(cis-α-PDP)Mo(NO)(CO)]PF(6) ([cis-α-3]PF(6)), [(cis-α-PDP)Mo(NO)Br]PF(6) ([4]PF(6)), [(trans-PDP)Cu](BF(4))(2)·CH(3)CN ([5](BF(4))(2)·CH(3)CN), and [(trans-PDP)Cu](OSO(2)CF(3))(2) ([5](OSO(2)CF(3))(2)) have been synthesized and structurally characterized by single-crystal X-ray diffraction. These are the first reported complexes of PDP on metal centers other than iron(II). The observed configurations indicate a broader range of accessible PDP topologies than has been reported. The {(cis-α-PDP)Mo(NO)}(+) fragment is found to be less π-basic than the dearomatizing {Tp(MeIm)Mo(NO)} fragment [Tp = hydridotris(1-pyrazolyl)borato; MeIm = 1-methylimidazole].     

Chloro half-sandwich osmium(II) complexes: influence of chelated N,N-ligands on hydrolysis, guanine binding, and cytotoxicity

Relatively little is known about the kinetics or the pharmacological potential of organometallic complexes of osmium compared to its lighter congeners, iron and ruthenium. We report the synthesis of seven new complexes, [(eta6-arene)Os(NN)Cl]+, containing different bidentate nitrogen (N,N) chelators, and a dichlorido complex, [(eta6-arene)Os(N)Cl2]. The X-ray crystal structures of seven complexes are reported: [(eta6-bip)Os(en)Cl]PF6 (1PF6), [(eta6-THA)Os(en)Cl]BF4 (2BF4), [(eta6-p-cym)Os(phen)Cl]PF6 (5PF6), [(eta6-bip)Os(dppz)Cl]PF6 (6PF6), [(eta6-bip)Os(azpy-NMe2)Cl]PF6 (7PF6), [(eta6-p-cym)Os(azpy-NMe2)Cl]PF6 (8PF6), and [(eta6-bip)Os(NCCH3-N)Cl2] (9), where THA = tetrahydroanthracene, en = ethylenediamine, p-cym = p-cymene, phen = phenanthroline, bip = biphenyl, dppz = [3,2-a: 2',3'-c]phenazine and azpy-NMe2 = 4-(2-pyridylazo)-N,N-dimethylaniline. The chelating ligand was found to play a crucial role in enhancing aqueous stability. The rates of hydrolysis at acidic pH* decreased when the primary amine N-donors (NN = en, t1/2 = 0.6 h at 318 K) are replaced with pi-accepting pyridine groups (e.g., NN = phen, t1/2 = 9.5 h at 318 K). The OsII complexes hydrolyze up to 100 times more slowly than their RuII analogues. The pK*a of the aqua adducts decreased with a similar trend (pK*a = 6.3 and 5.8 for en and phen adducts, respectively). [(eta6-bip)Os(en)Cl]PF6/BF4 (1PF6/BF4) and [(eta6-THA)Os(en)Cl]BF4 (2BF4) were cytotoxic toward both the human A549 lung and A2780 ovarian cancer cell lines, with IC50 values of 6-10 microM, comparable to the anticancer drug carboplatin. 1BF4 binds to both the N7 and phosphate of 5'-GMP (ratio of 2:1). The formation constant for the 9-ethylguanine (9EtG) adduct [(eta6-bip)M(en)(9EtG)]2+ was lower for OsII (log K = 3.13) than RuII (log K = 4.78), although the OsII adduct showed some kinetic stability. DNA intercalation of the dppz ligand in 6PF6 may play a role in its cytotoxicity. This work demonstrates that the nature of the chelating ligand can play a crucial role in tuning the chemical and biological properties of [(eta6-arene)Os(NN)Cl]+ complexes.     

Solution and solid-state dynamics of metal-coordinated white phosphorus

The dynamic behavior in solution of eight mono-hapto?tetraphosphorus transition metal-complexes, trans-[Ru(dppm)(2) (H)(η(1) -P(4) )]BF(4) ([1]BF(4) ), trans-[Ru(dppe)(2) (H)(η(1) -P(4) )]BF(4) ([2]BF(4) ), [CpRu(PPh(3) )(2) (η(1) -P(4) )]PF(6) ([3]PF(6) ), [CpOs(PPh(3) )(2) (η(1) -P(4) )]PF(6) ([4]PF(6) ), [Cp*Ru(PPh(3) )(2) (η(1) -P(4) )]PF(6) ([5]PF(6) ), [Cp*Ru(dppe)(η(1) -P(4) )]PF(6) ([6]PF(6) ), [Cp*Fe(dppe)(η(1) -P(4) )]PF(6) ([7]PF(6) ), [(triphos)Re(CO)(2) (η(1) -P(4) )]OTf ([8]OTf), and of three bimetallic Ru(μ,η(1:2) -P(4) )Pt species [{Ru(dppm)(2) (H)}(μ,η(1:2) -P(4) ){Pt(PPh(3) )(2) }]BF(4) ([1-Pt]BF(4) ), [{Ru(dppe)(2) (H)}(μ,η(1:2) -P(4) ){Pt(PPh(3) )(2) }]BF(4) ([2-Pt]BF(4) ), [{CpRu(PPh(3) )(2) )}(μ,η(1:2) -P(4) ){Pt(PPh(3) )(2) }]BF(4) ([3-Pt]BF(4) ), [dppm=bis(diphenylphosphanyl)methane; dppe=1,2-bis(diphenylphosphanyl)ethane; triphos=1,1,1-tris(diphenylphosphanylmethyl)ethane; Cp=η(5) -C(5) H(5) ; Cp*=η(5) -C(5) Me(5) ] was studied by variable-temperature (VT) NMR and (31) P{(1) H} exchange spectroscopy (EXSY). For most of the mononuclear species, NMR spectroscopy allowed to ascertain that the metal-coordinated P(4) molecule experiences a dynamic process consisting, apart from the free rotation about the M?P(4) axis, in a tumbling movement of the P(4) cage while remaining chemically coordinated to the central metal. EXSY and VT (31) P?NMR experiments showed that also the binuclear complex cations [1-Pt](+) -[3-Pt](+) are subjected to molecular motions featured by the shift of each metal from one P to an adjacent one of the P(4) moiety. The relative mobility of the metal fragments (Ru vs. Pt) was found to depend on the co-ligands of the binuclear complexes. For complexes [2]BF(4) and [3]PF(6) , MAS, (31) P?NMR experiments revealed that the dynamic processes observed in solution (i.e., rotation and tumbling) may take place also in the solid state. The activation parameters for the dynamic processes of complexes 1(+) , 2(+) , 3(+) , 4(+) , 6(+) , 8(+) in solution, as well as the X-ray structures of 2(+) , 3(+) , 5(+) , 6(+) are also reported. The data collected suggest that metal-coordinated P(4) should not be considered as a static ligand in solution and in the solid state.     

Pyridine substituted N-heterocyclic carbene ligands as supports for Au(I)-Ag(I) interactions: formation of a chiral coordination polymer

Reaction of 1,3-bis(2-pyridinylmethyl)-1H-imidazolium tetrafluoroborate, [H(pyCH(2))(2)im]BF(4), with silver oxide in dichloromethane readily yields [Ag((pyCH(2))(2)im)(2)]BF(4), 1.BF(4)(). 1.BF(4) is converted to the analogous Au(I)-containing species, [Au((pyCH(2))(2)im)(2)]BF(4), 3, by a simple carbene transfer reaction in dichloromethane. Further treatment with two equivalents of AgBF(4) produces the trimetallic species [AuAg(2)((pyCH(2))(2)im)(2)(NCCH(3))(2)](BF(4))(3), 4, which contains two silver ions each coordinated to the pyridine moieties on one carbene ligand and to an acetonitrile molecule in a T-shaped fashion. Monometallic [Ag((py)(2)im)(2)]BF(4), 5, and [Au((py)(2)im)(2)]BF(4), 6, are made analogously to 1.BF(4) and 3 starting from 1,3-bis(2-pyridyl)-imidazol-2-ylidene tetrafluoroborate, [H(py)(2)im]BF(4). Addition of excess AgBF(4) to 6 yields the helical mixed-metal polymer, ([AuAg((py)(2)im)(2)(NCCH(3))](BF(4))(2))(n), 7 which contains an extended Au(I)-Ag(I) chain with short metal-metal separations of 2.8359(4) and 2.9042(4) A. Colorless, monometallic [Hg((pyCH(2))(2)im)(2)](BF(4))(2), 8, is easily produced by refluxing [H(pyCH(2))(2)im)]BF(4) with Hg(OAc)(2) in acetonitrile. The related quinolyl-substituted imidazole, [H(quinCH(2))(2)im]PF(6), is produced analogously to [H(pyCH(2))(2)im]BF(4). [Hg((quinCH(2))(2)im)(2)](PF(6))(2), 9, is isolated in good yield as a white solid from the reaction of Hg(OAc)(2) and [H(quinCH(2))(2)im]PF(6). The reaction of [H(quinCH(2))(2)im]PF(6) with excess Ag(2)O produces the triangulo-cluster [Ag(3)((quinCH(2))(2)im)(3)](PF(6))(3), 11. All of these complexes were studied by (1)H NMR spectroscopy, and complexes 3-9 were additionally characterized by X-ray crystallography. These complexes are photoluminescent in the solid state and in solution with spectra that closely resemble those of the ligand precursor.     

First correlation of nanoparticle size-dependent formation with the ionic liquid anion molecular volume

Stable silver nanoparticles are obtained reproducibly by hydrogen reduction of different inorganic precursors from AgIX salts (X = BF4, PF6, OTf) dissolved in the ionic liquids BMim+BF4-, BMim+PF6-, BMim+OTf-, or BtMA+NTf2- [BMim+ = n-butylmethylimidazolium, BtMA+ = n-butyltrimethylammonium, NTf2 = N(O2SCF3)2, and OTf = O3SCF3] in the presence of n-butylimidazole (Bim) as the scavenger for the HX acid byproduct and with a narrow size distribution in the diameter range of 2.8-26.1 nm, which increases linearly with the molecular volume of the ionic liquid anion (transmission electron microscopy characterization).     

Reactivity and catalytic activity of a robust ruthenium(II)-triphos complex

The ruthenium(II)-triphos acetato complex [RuCl(OAc)(kappa3-triphos)] (triphos = (PPh2CH2)3CMe) has been found to be an active catalyst precursor for the hydrogenation of 1-alkenes under relatively mild conditions (5-50 bar H2, 50 degrees C). In contrast to related triphenylphosphine complexes, [RuCl(OAc)(kappa3-triphos)] is much less air sensitive and high catalytic activities were achieved when catalyst samples were prepared without exclusion of air or moisture. Substitution of the acetato ligand can be effected by treatment of acid, affording [Ru2(mu-Cl)3(kappa3-triphos)2]Cl and [RuCl(kappa3-triphos)]2(BF4)2 with aqueous HCl and [Et2OH]BF4, respectively, or by heating with dmpm in the presence of [NH4]PF6, resulting in formation of [RuCl(kappa2-dmpm)(kappa3-triphos)]PF6 (dmpm = PMe2CH2PMe2). A hydride complex, [RuHCl(kappa3-triphos)], formed by acetato-mediated heterolytic cleavage of dihydrogen is proposed as the active catalytic species. An inner-sphere, monohydride mechanism is suggested for the catalytic cycle, with chloro and triphos ligands playing a spectator role. These mechanistic proposals are consistent with reactivity studies carried out on [RuCl(OAc)(kappa3-triphos)] and [RuH(OAc)(kappa3-triphos)] and supported by a computational analysis. The solid-state structures of [RuCl(OAc)(kappa3-triphos)], [RuCl(kappa3-triphos)]2(BF4)2, and [RuCl(kappa2-dmpm)(kappa3-triphos)]PF6 have been established by X-ray diffraction.     

Thermodynamic modeling of the phase behavior of binary systems of ionic liquids and carbon dioxide with the group contribution equation of state

The group contribution equation of state (GC-EOS) was applied to predict the phase behavior of binary systems of ionic liquids of the homologous families 1-alkyl-3-methylimidazolium hexafluorophosphate and tetrafluoroborate with CO2. Pure group parameters for the new ionic liquid functional groups [-mim][PF6] and [-mim][BF4] and interaction parameters between these groups and the paraffin (CH3, CH2) and CO2 groups were estimated. The GC-EOS extended with the new parameters was applied to predict high-pressure phase equilibria in binary mixtures of the ionic liquids [emim][PF6], [bmim][PF6], [hmim][PF6], [bmim][BF4], [hmim][BF4], and [omim][BF4] with CO2. The agreement between experimental and predicted bubble point data for the ionic liquids was excellent for pressures up to 20 MPa, and even for pressures up to about 100 MPa, the agreement was good. The results show the capability of the GC-EOS to describe phase equilibria of systems consisting of ionic liquids.