MXn和TPPTS.Ln体系催化1—已烯氢甲酰化反应的新探索

在可比条件下,研究了新型水溶性膦配体TOPPTS。Ln(TPPTS=三（间碘酸基苯基）膦,Ln=Y,La,Nd,Ho,Yb)分别与RhCl3、NiCl2、PbCl2组成的体系催化1-已烯氢甲酰化反应。结果表明,TPPTS。Ln-RhCl3(Ln-Y、Ho)的催化活性优于TPPTS。Na3-RhCl3体系（1-已烯的转化率分别为49.9%、38.8%、24.3%）,有意义的是,TPPTS。Yb-NiCl2体系（转化率44.5%)亦高于TPPTS。Na3-RhCl3体系的催化结果,且稀土离子介入溶性膦配体后,使催化剂支支链醛的选择性明显提高。     

水溶性钌-氢配合物催化1-已烯双键异构化反应研究

研究了水溶性钌-氢配合物RuHCl(TPPTS)3在水/有机两相体系中催化1-己烯双键异构化反应.考察了反应温度、时间、膦配体浓度、相转移催化剂CTAB浓度以及底物与催化剂摩尔比等对转化率和产物选择性的影响.在最佳条件下1-己烯转化率达到82.4%,2-己烯选择性21.2%,3-己烯61.2%,没有发现骨架异构化.催化剂可重复使用5次.     

两相催化体系中双子表面活性剂对1-十二烯氢甲酰化反应的促进作用

报道了水溶性铑膦配合物组成的复合催化体系催化1-十二烯氢甲酰化反应中,双子表面活性剂[二溴化-(N,N,N′,N′-四甲基)-N,N′-二(十六烷基)-乙二铵]形成胶束的助催化作用.结果表明,在水/有机两相中,双子表面活性剂比单链表面活性剂CTAB具有更好加速催化反应的作用,并使烯烃氢甲酰化的区域选择性显著提高.这归因于双子表面活性剂有较低的cmc,可形成更加紧密规整的胶束结构,有利于增溶在胶束中的烯烃与铑催化剂配位和生成正构醛.     

两相催化体系中双子表面活性剂对1-十二烯氢甲酰化反应的助催化作用

合成了几种具有刚性连接基团的双子表面活性剂,研究了它们在Rh-TPPTS体系中催化长链烯烃氢甲酰化反应中的助催化作用.结果表明,在水/有机两相催化体系中,新型双子表面活性剂的助催化作用比单链表面活性剂CTAB更好,在较低的表面活性剂浓度下能得到较高的反应转化率.这归因于此类表面活性剂有较低的cmc,降低界面张力的能力和对1-十二烯的增溶能力比CTAB更强.     

1-丁烯氢甲酰化反应的宏观动力学研究

采用三苯基膦羰基氢化铑作为催化剂,进行1-丁烯氢甲酰化合成戊醛反应,主要考察温度、铑浓度、配体浓度、丁烯浓度、合成气中H2和CO分压等因素对反应速率的影响.动力学研究表明温度、Rh浓度、丁烯浓度和H2分压的增加均可提高反应速度,CO分压和配体量的增加使反应速度降低.给出了RhH(CO)(PPh3)3催化1-丁烯氢甲酰化的反应动力学方程,并采用非线性最小二乘法对模型进行参数估值,计算值与实验值具有较好的一致性.     

水溶性铑－膦配合物催化1－十二碳烯常压氢甲酰化反应研究

本文研究了水溶性铑配合物ＲｈＣｌ（ＣＯ）（ＴＰＰＴＳ）２在常压（ＣＯ：Ｈ２＝１：１）条件下对１－十二碳烯氢甲酰化反应的催化性能，并对催化剂浓度、表面活性剂浓度、溶液ｐＨ值、膦铑比、溶剂等因素的变化对催化活性的影响作了考察．结果表明，表面活性剂（ＣＴＡＢ）的加入，可以在反应体系中形成胶束．加速有机相和水相间的传质速度，从而提高催化转化速度．在反应温度（８０℃）下，ＣＴＡＢ的临界胶束浓度（ＣＭＣ）较室温下高．达到最佳催化活性的ｐＨ范围为７～９，［Ｐ］／［Ｒｈ］比为１６，而有机溶剂的加入则使转化数降低．     

单膦及双膦配体铑络合物催化的莰烯氢甲酰化反应

莰烯的氢甲酰化(100℃,10 MPa CO+H_2)因铑-膦络物中膦配体的不同而给出完全不同的产物.圆锥角较大的膦配体倾向于给出更多的exo-产物.双齿膦配体圆锥角虽较小,但因生成双膦桥联的铑络合物而使加氢能力下降,所以只得到较低转化率的endo-莰基醛.本文还以红外光谱研究了活性催化物种并讨论了exo-,endo-产物的生成机制.     

高活性离子液体-铑膦络合物体系催化1-己烯氢甲酰化反应

 The hydroformylation of 1-hexene catalyzed by rhodium-TPPTS complexes in the ionic liquid [bmim]BF4 was studied. The activity and selectivity of the rhodium-TPPTS complexes in [bmim]BF4 were much higher than those reported in other ionic liquids. The TOF of 1-hexene and selectivity for aldehyde were 1508 h-1 and 92%, respectively, under the optimum conditions. The high activity of the catalyst is ascribed to the absence of halide ions as well as the much higher solubility of hydrogen and rhodium-TPPTS complexes in [bmim]BF4 than in [bmim]PF6.     

新型配体三 (3,4-二甲氧基苯基) 膦的合成及其 Rh 配合物在 1-十二烯氢甲酰化反应中的催化性能

 将合成的三 (3,4-二甲氧基苯基) 膦 (TDMOPP) 用作 Rh 催化剂配体, 并用于 1-十二烯氢甲酰化反应, 考察了膦/铑比和反应温度对 Rh-TDMOPP 催化剂活性和选择性的影响. 结果表明, 在膦/铑比与反应温度较低时, Rh-TDMOPP 活性是 Rh-三苯基膦催化剂的 3 倍.     

Catalytic oxidation of 1-hexene with molecular oxygen by iridium nitro complexes

The oxidation of 1-hexene by molecular oxygen catalyzed by iridium(III) complexes, [Ir(CH₃CN)_5−xCl_x(NO₂)]^2−x (x=0, 1, or 2) has been studied in acetonitrile under P(O₂)=1.5 atm and T=100°C. [Ir(CH₃CN)₅(NO₂)](PF₆)₂ oxidizes 1-hexene to 1,2-epoxyhexane. Complex [Ir(CH₃CN)₄Cl(NO₂)]PF₆ oxidizes 1-hexene to 2,3-epoxyhexane only in the presence of [Pd(PhCN)₂(Cl)₂] (an olefin activator). In contrast to the cationic complexes, the neutral complex [Ir(CH₃CN)₄Cl₂(NO₂)] oxidizes 1-hexene to 2-hexanone only in the presence of [Pd(PhCN)₂(Cl)₂].     

Rhodium complexes with dioximes as catalysts of hydroformylation and hydrogenation of 1-hexene

Rhodium(II) complexes with dioximes [Rh(Hdmg)₂(PPh₃)]₂ [I] (Hdmg=monoanion of dimethylglyoxime) and [Rh(Hdmg)(ClZndmg)(PPh₃)]₂ [II] catalyse hydroformylation and hydrogenation reactions of 1-hexene at 1 MPa CO/H₂ and 0.5 MPa H₂ at 353 K, respectively. Hydroformylation with complex [I] produces 94% of aldehydes (n/iso=2.2) and 6% 2-hexene whereas the second catalyst [II] gives ca. 40% of aldehydes (n/iso=2.1) and 60% of 2-hexene. Corresponding Rh(III) complexes are inactive in hydroformylation except of RhH(Hdmg)₂(PPh₃) [III], which shows activity similar to [I]. Complexes [Rh(Hdmg)₂(PPh₃)]₂ [I], [Rh(Hdmg)(ClZndmg)(PPh₃)]₂ [II], RhH(Hdmg)₂(PPh₃) [III] and [Rh(Hdmg)₂(PPh₃)₂]ClO₄ [V] catalyse 1-hexene hydrogenation with an average TON ca. 18 cycles/mol [Rh]×min. Complex [II] has also been found to catalyse hydrogenation of cyclohexene, 1,3-cyclohexadiene and styrene.     

Rhodium phosphine complexes immobilized on silica as active catalysts for 1-hexene hydroformylation and arene hydrogenation

In immobilizing the rhodium complexes [Rh(acac)(CO)(P)] (1) and [Rh(acac)(P)₂] (2) (P = Ph₂PCH₂CH₂Si(OMe)₃) onto SiO₂, acetylacetone is found to be released through protonation of the acac ligand by the acidic silica-OH groups. The resulting complexes [Rh(O-{SiO₂}(HO-{SiO₂})(CO)(P-{SiO₂})] (1a) and [Rh(O-{SiO₂})(HO-{SiO₂})(P-{SiO₂})₂] (2a) were successfully tested with respect to their catalytic action on 1-hexene hydroformylation as well as benzene and toluene hydrogenation. The reaction outcome, viz. the formation of aldehydes versus isomerization, depends strongly on the presence and concentration of a phosphine co-catalyst. Thus, while 1a gave only a 17% yield of aldehyde in the absence of phosphines, the yield is increased to 54% in the presence of phosphinated silica P-{SiO₂} or even 94% if PPh₃ is added to the solution. Without extra added phosphine, both 1a and 2a effect mainly the isomerization of 1-hexene to 2-hexene. Pre-catalyst 1a catalyzes also the hydrogenation of benzene at 10.5 atm H₂ and 90 °C to give cyclohexane with a TOF of 608 h⁻¹.     

Recycle and recovery of rhodium complexes with water-soluble and amphiphilic phosphines in ionic liquids for hydroformylation of 1-hexene

A biphasic catalysis system composed of ionic liquid and rhodium complexes with water-soluble or amphiphilic phosphine ligands bearing water-soluble groups of sodium sulfonate have been employed for hydroformylation of 1-hexene. The experimental results show that the activity is almost independent of the hydrotropicity of the phosphine ligands in BMI·BF₄. In this system, the extraction of phosphine species by the organics from the IL phase was quite low but larger than that of rhodium species and showed rather good stability of catalytic activity. A slight decrease in the aldehyde n/i ratio during the catalyst reuse could be recovered, in part, by replenishing certain amount of ligand into the used catalyst system.     

Transformation of rhodium carbonyl complexes in hydroformylation of 1-hexene studied fromin situ IR spectroscopic data

Rhodium carbonyl complexes that formed from RhCl₃·4H₂O and RhCl₃·4H₂O modified by poly-N,N-dimethyl-N,N-diallylammonium chloride in a methanol—chloroform medium in the hydroformylation of 1-hexene were studied byin situ IR spectroscopy. Along with the rhodium hydrocarbonyl complexes, anionic complexes of the [Rh(CO)₂Cl₂]⁻ type, whose concentrations and rates of formation in an acidic medium are much higher than those in a basic medium, were shown to be the active centers of hydroformylation. The function of the polycation is the stabilization of the catalytically active mononuclear rhodium complexes. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 708–710, April, 1999.     

Polymeric rhodium-containing catalysts in olefin hydroformylation

The main results obtained by studying hydroformylation of olefins on polymeric rhodium-containing catalysts are reviewed. Different types of N-containing polymeric ligands capable of hydroformylating under conditions of heterogeneous catalysis are considered. Possibilities of using water-soluble polymers containing quaternary ammonium groups are shown. The data on the influence of a polymeric matrix on the catalytic properties of the rhodium catalyst of olefin hydroformylation are presented.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2346–2351, November, 2004.     

Trichlorostannyl complexes of iridium with both P-donor and N-donor ligands: Preparation and activity as hydrogenation catalysts

Bis(trichlorostannyl) complex IrH(SnCl₃)₂(PPh₃)₂ (1) was prepared by allowing the chloro-derivative IrHCl₂(PPh₃)₃ to react with SnCl₂·2H₂O in ethanol. Instead, treatment of phosphite complexes IrHCl₂P₃ [P = P(OEt)₃ and PPh(OEt)₂] with SnCl₂·2H₂O gave stannyl derivatives IrCl₂(SnCl₃)P₃ (2). Pyrazole-trichlorostannyl complexes IrHCl(SnCl₃)(HRpz)P₂ (3, 4) (R = H, 3-Me; P = PPh₃, PⁱPr₃) were prepared by allowing chloro-derivatives IrHCl₂(HRpz)P₂ to react with SnCl₂·2H₂O. 1,2-Bipyridine-trichlorostannyl complexes IrHCl(SnCl₃)(bpy)P (5) (P = PPh₃, PⁱPr₃) were also prepared. Complexes 1-5 were characterised spectroscopically (IR, ¹H, ³¹P, ¹¹⁹Sn NMR) and a geometry in solution was also established. The trichlorostannyl iridium complexes were evaluated as catalyst precursors for the hydrogenation of 2-cyclohexen-1-one and cinnamaldehyde. The influence of the stannyl group, as well as the steric hindrance of both N-donor and P-donor ligands in the catalytic activity of the complexes is discussed.     

Application of heteroleptic iridium complexes with fluorenyl-modified 1-phenylisoquinoline ligand for high-efficiency red polymer light-emitting devices

A series of new heteroleptic iridium complexes bearing fluorenyl-modified 1-phenylisoquinoline as the first ligand and different ancillary ligands has been prepared and characterized. These complexes bis(1-(3-(9,9-dimethyl-fluoren-2-yl)phenyl)isoquinoline-C2,N′)iridium(III)acetylacetonate(Ir(DMFPQ)₂acac)), bis(1-(3-(9,9-dimethyl-fluoren-2-yl)phenyl)isoquinoline-C2,N′)iridium(III)(3-(pyridin-2-yl)-1,2,4-triazolate)(Ir(DMFPQ)₂pt) and bis(1-(3-(9,9-dimethyl-fluoren-2-yl)phenyl)isoquinoline-C2,N′)iridium(III)(2-(2-pyridyl)benzimidazolate)(Ir(DMFPQ)₂pbi) showed red phosphorescent emissions of 615-630 nm in dichloromethane solution. The device fabricated with these complexes doped into a host polyfluorene (PFO) blend with 30% of an electron transport material 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD) showed high device efficiencies. Ir(DMFPQ)₂acac exhibited red emission with an external quantum efficiency(η_ext) of 14.3% and luminous efficiency(η_c) of 7.8 cd/A at 1.2 mA/cm² and the maximum brightness reached 10 006 cd/m² (Commission Internationale de I’Eclairage(CIE) chromaticity coordinates: (0.67, 0.32)) at 412 mA/cm². Ir(DMFPQ)₂pt showed a η_ext of 13.0% and η_c of 9.2 cd/A at 17 mA/cm², 1532 cd/m², and the maximum brightness reached 15085 cd/m² (CIE: 0.64, 0.34) at 360 mA/cm².     

Hydroformylation of 1-hexene in the presence of rhodium complexes immobilized on polyorganosiloxanes

It was demonstrated that the catalyst system based on acacRh(CO)₂ and polyorgano-siloxanes exhibits high activity and stability in hydroformylation of 1-hexene. The effects of the nature of the oligomer, the ratio of oligomers, and the oligomer: rhodium ratio in the polymer on the synthesis and catalytic properties of the system were studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1155–1157, June, 1997.     

Preparation of rhodium–phyllosilicate catalysts without leaching in liquid-phase 1-hexene hydrogenation

Rhodium catalysts have been prepared on palygorskite and montmorillonite (clay) supports by reduction with hydrogen (1 atmosphere) at room temperature of a cationic organometallic rhodium compound anchored to the support. The activity of these catalysts for the hydrogenation of liquid-phase 1-hexene remains constant with increase of prehydrogenation time and with re-use for several runs. No rhodium leaching is observed.