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本文研究了两种水溶性钌-膦配合物RuCl_2(TPPTS)_3和Rucl_2(CO)_2(TPPTS)_2[TPPTS为:P(m-C_6H_4SO_3Na)_3]的合成,在水相和有机相组成的两相催化体系中,考察了它们衍生出的活性物种和以RuCl3-TPPTS原位合成的活性物种对肉桂醛的选择加氢性能,并对反应温度(20—80℃),氢压(2—6MPa),催化剂浓度(1.12×10~(-3)~4.50×10~(-3)mol/L),配体TPPTS浓度(9.0×10~(-3)~5.4×10~(-2)mol/L),表面活性剂浓度和反应时间的变化对选择加氢反应的影响进行了详细研究。实验结果表明,RuCl_3-TPPTS原位合成配合物的催化加氢活性最高,而在金属Ru上羰基的配位将使加氢活性降低,表面活性剂CTAB是有效的促进剂,它的加入可大大提高加氢活性,选择适当的CTAB浓度,在反应结束后水相与有机相分层迅速,有利于Ru催化剂的分离,在所考察的反应条件下,肉桂醛选择加氢生成肉桂醇的转化率大于80%,选择性达96%以上。 相似文献
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研究了水溶性钯-膦配合物PdCl2(TPPTS)2催化1-己烯加氢反应,考察了两相催化体系中添加表面活性剂CTAB,膦配体TPPTS,以及溶液pH值等对反应的影响,证明了1-己烯加氢反应中有一诱导期.反应中涉及两种催化活性物种.一种是由PdCl2(TPPTS)2还原生成的低氧化态催化物种,它在一定的CTAB浓度下,可以保持相当的稳定性.另一种是被TPPTS或H2还原形成的钯黑.根据PdCl2和TPPTS反应过程的31PNMR研究,对PdCl2(TPPTS)2分子中Pd被还原和TPPTS被氧化提出了解释 相似文献
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水溶性钯—膦配合物催化1—己烯加氢反应研究 总被引:1,自引:2,他引:1
研究了水溶性钯-膦配合物PdCl2(TPPTS)2催化1-己烯加氢反应,考察了两相催化体系中添加表面活性剂CTAB,膦配体TPPTS,以及溶液PH值等对反应的影响。证明了1-己烯加氢反应中有一诱导期。反应中涉及两种催化活性物种。 相似文献
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合成了两种水溶性铱膦配合物,IrCl(CO)-(TPPTSW)2和HIrCl2(CO)(TPPTS)2「TPPTS=P(m-C6H4SO4Na)3」,并且在两相催化反应体系中评价了它们对苯乙烯加氢活性,考察了反应温度,压力,两种相转移试剂CCTAB和β-CD浓度变化对苯乙烯加氢转化率的影响。 相似文献
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RuCl2(Ph3P)4或RuCl2(DMSO)4在甲苯中直接与等摩尔的亚胺膦配体N,N-双-[邻-(二苯基膦苯亚甲基)]乙二胺(P2N2)在甲苯中回流反应,高产率地合成了反式配位的双亚胺双膦钌配合物trans-RuCl2P2N2.在温和条件下,该配合物作为新型催化剂有效地催化α,β-不饱和酸和几种功能团烯烃的选择加氢反应.讨论了可能的催化活性物种. 相似文献
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水溶性铑—膦配合物催化长链烯烃氢甲酰化反应研究—反应条件的影响 总被引:10,自引:3,他引:10
本文研究了两相催化体系中,在CTAB(C16H33NMe3Br)存在下,水溶性铑-膦配合物RhCl(CO)(TPPTS)2对1-己烯氢甲酰化反应的催化性能,详细考察了反应温度、压力、膦/铑比等对催化活性的影响。结果表明,在1.0MPa恒压下,反应温度100℃,膦/铑摩尔比为16,H2:CO=1:1的条件下,1-己烯氢甲酰化的转化频率(TOF)可达到39.8min^-1。在此反应条件下,有机相和水相 相似文献
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在THF溶液中,40-60℃及0.3-0.5MPa氢压条件下,「RuCl2(cht)」2+(S)-BINAP手性催化主本系催化不饱和手性缩酮2选择加氢,再经脱去手性二醇,即可高立体选择地制得(R)-3-甲基环十五烷酮(4),(R)-(-)-麝香酮),化学收率≥95%, 相似文献
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采用快速混合停流技术,考察了在实际反应条件下,不同锰卟啉配合物MnⅢ(Por.)Cl(Por.=TPP、TMOPP和TFPP)与单氧给体PhIO构建的细胞色素P-450模拟酶体系催化活性物种的生成及催化烯烃环氧化过程.在氧给体PhIO作用下,MnⅢ(Por.)Cl均生成了高价锰氧卟啉配合物和双核μ-氧锰卟啉配合物;但MnⅢ(TPP)Cl和MnⅢ(TMOPP)Cl存在严重的氧化分解,而MnⅢ(TFPP)Cl不易氧化分解,且它的催化环氧化活性最高. 相似文献
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苯乙烯-丁二烯-苯乙烯三嵌段共聚物新型加氢催化剂的研究 总被引:4,自引:0,他引:4
烯烃加氢得到烷烃,从化学热力学角度判断这个反应可以进行,由于氢分子相当稳定,HH键不易受极化的影响而断裂,实际上,如果没有催化剂的存在,反应是很难进行的.各种过渡金属,例如铂、钯、铑、钴、铱和镍等都具有未充满和不稳定的d电子轨道,容易吸附大量的氢并使其活化,从而很容易对许多基团进行氢化反应.钌/二烯烃/氢气反应体系就符合上述原理,苯乙烯丁二烯苯乙烯三嵌段共聚物(SBS)就属二烯烃类共聚物,由于这类共聚物中存在CC不饱和双键,在日光、紫外光、热等环境下,其耐侯性和热稳定性不好,限制了它在更广泛… 相似文献
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A variety of 3-substituted benzisoxazoles were reduced with hydrogen using the chiral ruthenium catalyst, {RuCl(p-cymene)[(R,R)-(S,S)-PhTRAP]}Cl. The ruthenium-catalyzed hydrogenation proceeded in high yield in the presence of an acylating agent, affording α-substituted o-hydroxybenzylamines with up to 57% ee. In the catalytic transformation, the N-O bond of the benzisoxazole substrate is reductively cleaved by the ruthenium complex under the hydrogenation conditions. The C-N double bond of the resulting imine is saturated stereoselectively through the PhTRAP-ruthenium catalysis. The hydrogenation produces chiral primary amines, which may work as catalytic poisons, however, the amino group of the hydrogenation product is rapidly acylated when the reaction is conducted in the presence of an appropriate acylating agent, such as Boc?O or Cbz-OSu. 相似文献
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Reduced graphene oxide (RGO) supported ruthenium (Ru) catalyst was prepared by an impregnation method using RuCI3 as a precursor and RGO as a support. The catalyst Ru/RGO was used for the selective hydrogenation ofp-chloronitrobenzene (p-CNB) to p-chloroaniline (p-CAN), showing a selectivity of 96% at complete conversion of p-CNB at 60 ℃ and 3.0 MPa H2. The Ru/RGO catalyst was extremely active for the hydrogenation of a series of nitroarenes, which can be attributed to the small sized and the fine dispersity of the Ru nanoparticles on the RGO sheets characterized by TEM. Moreover, the catalyst also can be recycled five times without the loss of activity. 相似文献
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利用氯甲基吡啶与咪唑反应制备了一系列含吡啶取代咪唑L1~L5,考察了所得咪唑衍生物与钌化合物在碱性条件下原位形成的氮杂卡宾钌络合物对苯胺与醇氢转移反应的催化活性.研究了碱的种类、钌前体、温度等对反应的影响,结果表明RuCl3 H2O/1-(2-吡啶甲基)-3-甲基碘化咪唑(L3)/KOH催化体系在185℃时对苯胺与乙二醇反应的催化活性较高,选择性生成N-羟乙基苯胺,TON(单位活性转化的底物分数)可达2130.此外,还考察了RuCl3 H2O/L3/KOH催化体系对苯胺与丁醇、环己醇、异丙醇、苯甲醇反应的催化性能.在催化剂作用下,醇与苯胺可形成亚胺及仲胺,伯醇可以自氢转移反应形成酯,反应产物的结构及选择性取决于醇的结构及反应条件. 相似文献
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研究了水/有机两相体系中TPPTS(磺化三苯基膦)氧化为OTPPTS(氧化的TPPTS)对Rh/TPPTS催化烯烃氢甲酰化反应的影响. 结果表明,在己烯-1、辛烯-1和十二烯-1氢甲酰化反应中,当n(OTPPTS)/n(TPPTS)<1时,对催化剂体系性能的影响较小,但当n(OTPPTS)/n(TPPTS)>1时,将引起催化剂体系的活性、选择性和稳定性下降; 如果保持体系中TPPTS的含量一定,使n(TPPTS)/n(Rh)≥18,当n(OTPPTS)/n(Rh)=20时,则对催化剂体系性能的影响不明显. 这说明生成的OTPPTS不是铑催化剂的毒物. TPPTS氧化为OTPPTS致使铑催化剂的活性和生成醛的选择性下降, 是由于TPPTS浓度的降低导致n(TPPTS)/n(Rh)值过低,使催化循环中各活性物种的平衡发生变化及铑配合物的稳定性变差所造成的结果. 相似文献
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Krause JO Nuyken O Wurst K Buchmeiser MR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(3):777-784
The synthesis and heterogenization of new Grubbs-Hoveyda type metathesis catalysts by chlorine exchange is described. Substitution of one or two chlorine ligands with trifluoroacetate and trifluoromethanesulfonate was accomplished by reaction of [RuCl(2)([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (IMesH(2) = 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene) with the silver salts CF(3)COOAg and CF(3)SO(3)Ag, respectively. The resulting compounds, [Ru(CF(3)SO(3))(2)([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (1), [RuCl(CF(3)SO(3))([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (2), and [Ru(CF(3)CO(2))(2)([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (3) were found to be highly active catalysts for ring-closing metathesis (RCM) at elevated temperature (45 degrees C), exceeding known ruthenium-based catalysts in catalytic activity. Turn-over numbers (TONs) up to 1800 were achieved in RCM. Excellent yields were also achieved in enyne metathesis and ring-opening cross metathesis using norborn-5-ene and 7-oxanorborn-5-ene-derivatives. Even more important, 3 was found to be highly active in RCM at room temperature (20 degrees C), allowing TONs up to 1400. Heterogeneous catalysts were synthesized by immobilizing [RuCl(2)([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] on a perfluoroglutaric acid derivatized polystyrene-divinylbenzene (PS-DVB) support (silver form). The resulting supported catalyst [RuCl(polymer-CH(2)-O- CO-CF(2)-CF(2)-CF(2)-COO)([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (5) showed significantly reduced activities in RCM (TONs = 380) compared with the heterogeneous analogue of 3. The immobilized catalyst, [Ru(polymer-CH(2)-O-CO-CF(2)-CF(2)-CF(2)-COO)(CF(3)CO(2))([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (4) was obtained by substitution of both Cl ligands of the parent Grubbs-Hoveyda catalyst by addition of CF(3)COOAg to 5. Compound 4 can be prepared in high loadings (160 mg catalyst g(-1) PS-DVB) and possesses excellent activity in RCM with TONs up to 1100 in stirred-batch RCM experiments. Leaching of ruthenium into the reaction mixture was unprecedentedly low, resulting in a ruthenium content <70 ppb (ng g(-1)) in the final RCM-derived products. 相似文献