Alkoxy substituted MeO-BIPHEP-type diphosphines ligands for asymmetric hydrogenation of aryl ketones

In this paper,a series of optically active MeO-BIPHEP-type ligands,（S）-6,6′-dimethoxy-2,2’-bis（di-p-alkoxyphenylphosphine）- 1,1′-biphenyl were synthesized and used to prepare the ruthenium complex.The effects of para-substituted were observed,the results showed that the ruthenium catalysts[diphosphine RuCl;diamine]containing both t-Bu and i-Pr substitutions have better activities and enantioselectivities than the non-substituted ruthenium catalysts in the asymmetric hydrogenation of acetophenone.

A novel thermoregulated phosphine ligand used for the Rh-catalyzed hydroformylation of mixed C_(11-12) olefins in aqueous/organic biphasic system

A novel thermoregulated phosphine ligand PhP(CHCHO)CH(n=22) was synthesized and used for the Rh-catalyzed hydroformylation of mixed Colefins in aqueous/organic biphasic system.Under the optimized conditions,pressure =5 MPa (H:CO=1:1),phosphine/Rh =13(molar ratio),reaction time =6 h and temperature =130℃,the conversion of Colefins and the yield of aldehyde are 99%and 94%,respectively.The catalyst retained in aqueous phase can be easily separated from the product-containing organic phase by simple phase separation and the catalytic activity remains almost constant after four consecutive cycles.

Synthesis of a New Type of Amphilic and Water - soluble Tertiary Phosphine Ligands Substituted by an Ethoxylated Phosphonic Acid Chain and Their Palladium Complexes

The highly water-soluble phosphine ligands Na2O3PCH2CH2NH(CH2CH2O)nCH2CH2N- (CH2PPh2)2 (n=1,2,3) were prepared by a new and simple route under mild conditions in good yield; the palladium (II) complexes of the ligands 3a~c with 2:1 or 4:1 -PPh2 to Pd2+ molar ratio were also prepared and characterized .

1,3-Dicarbonyl compounds as phosphine-free ligands for Pd-catalyzed Heck and Suzuki reactions

Some 1,3-dicarbonyl compounds (such as pentane-2,4-dione and 3-oxo-N-phenylbutanamide) were found to constitute highly efficient, yet low-priced and phosphine-free ligands for the Pd-catalyzed Heck and Suzuki reactions of aryl bromides and iodides with very high turnover numbers (ca. 103–104).

Synthesis of novel chiral phosphine-triazine ligand derived fromα-phenylethylamine for Pd-catalyzed asymmetric allylic alkylation

A novel chiral phosphine-triazine ligand was synthesized from chiral α-phenylethylamine through a three-step procedure. In a model reaction of Pd-catalyzed allylic alkylation of rac-1,3-diphenylprop-2-en-1-y1 pivalate with dimethyl malonate, good enantioselectivity （90% e.e.） was obtained by using this ligand.

Efficient and recyclable Rh-catalytic system with involvement of phosphine-functionalized phosphonium-based ionic liquids for tandem hydroformylation—acetalization

The phosphine-functionalized phosphonium-based ionic liquids(dppm-Q, dppe-Q, dppp-Q and dppb-Q) as the bi-functional ligands enable the efficient one-pot tandem hydroformylationeacetalization. It was found that, in dppm-Q, dppe-Q, dppp-Q and dppb-Q, the incorporated phosphino-fragments were responsible for Rh-catalyzed hydroformylation and the phosphoniums were in charge of the subsequent acetalization as the Lewis acid catalysts. Moreover, the diphosphonium-based ionic liquid of dppb-DQ could be applied as a co-solvent to immobilize the Rh/dppb-Q catalytic system with the advantages of the improved catalytic performance, the available catalyst recyclability, and the wide generality for the substrates.

4-Amino-1,2,4-triazole Resin-supported Palladium Complex as Phosphine-free Catalyst for Suzuki Reaction in Aqueous Phase

1 Introduction The Suzuki cross-coupling reaction is a powerful and versatile method for the generation of unsymmetrical biaryls from arylboronic acids and aryl halides in a single step. However, the reaction is usually performed in the presence of Pd catalyst along with phosphine ligand, which sometimes creates practical problems because organophosphines tend to be expensive, poisonous, and air sensitive. Recently, phos-phine-free ligands,

一种高选择性联吡啶双膦配体在烯烃氢甲酰化中的应用研究

本研究以联吡啶为骨架合成了一种双齿膦配体BiPyPhos,通过核磁共振波谱、高分辨质谱和红外分析证实了双膦配体的结构。该配体的设计充分考虑了联吡啶骨架中N原子对骨架电子效应的调节作用,以及对铑配合物结构的调控能力。进一步的催化性能测试表明,该配体与铑原位形成的均相催化剂在催化端烯烃和内烯烃等底物时表现出优异的催化活性、化学选择性和区域选择性。例如,在1-辛烯氢甲酰化反应中,底物转化率高达100.0%,成醛选择性达到88.6%,其正异比高达43。该配体具有柔变的骨架和大的自然咬角,有利于形成空间位阻较小的直链烷基-铑活性物种,从而实现对区域选择性的调控。配体BiPyPhos的成功应用为羰基化反应催化剂的设计与合成提供了新的思路。

聚醚功能化离子液体辅助不对称氢化合成D-泛解酸内酯

为了解决手性催化剂在不对称氢化中难以循环利用的问题,本研究基于氨基酸和咪唑鎓盐离子液体修饰的手性吡咯烷基双膦配体,采用聚醚胍盐离子液体辅助铑催化酮基泛解酸内酯均相不对称氢化合成D-泛解酸内酯。研究了铑催化剂前体、双膦配体结构、溶剂效应和聚醚离子液体掺杂对催化活性和对映选择性的影响。基于筛选出的最佳双膦配体,构建出“均相催化-液/固分离”体系用于手性催化剂的分离和循环。结果表明:该催化体系表现出较高的催化活性、对映选择性和长期稳定性,经过5次循环后未见催化性能有明显下降,为不对称氢化合成D-泛解酸内酯的可行性提供了理论和实验依据。

钯催化膦配体的Suzuki-Miyaura偶联

Suzuki-Miyaura反应是应用最广泛的交叉偶联反应之一,因此其研究具有重要的意义。目前,通过碳磷键的断裂实现Suzuki-Miyaura反应的研究鲜有报道。本研究旨在研究钯催化膦配体的Suzuki-Miyaura反应,通过膦试剂的筛选、催化剂的筛选、溶剂的筛选、溶剂浓度考察和反应温度考察,探究了各种反应参数对反应结果的影响。最优反应条件是:在Schlenk反应管中依次加入4,5-双(二苯基膦)-9,9-二甲基氧杂蒽(Xantphos)、二(乙酰丙酮)钯(Pd(acac)_(2))、对甲氧基苯硼酸(4-Methoxyphenylboronic acid)和3-戊酮(DEK),并于100℃下搅拌24 h。

Highly luminescent and stable CsPbBr3 perovskite quantum dots modified by phosphine ligands

All-inorganic cesium lead halide perovskite quantum dots (QDs) have been a promising candidate for optoelectronic devices in recent years,such as light-emitting diodes,photodetectors and solar cells,owing to their superb optoelectronic properties.Still,the stability issue of nanocrystals is a bottleneck for their practical application.Herein,we report a facile method for the synthesis of a series of phosphine ligand modified CsPbBr3 QDs with high PL intensity.By introducing organic phosphine ligands,the tolerance of CsPbBr3 QDs to ethanol,water and UV light was dramatically improved.Moreover,the phosphine ligand modified QD films deposited on the glass subtracts exhibit superior PL intensity and optical stability to those of pristine QD based films.

Influence of bidentate structure of an aryl phosphine oxide ligand on photophysical properties of its Eu~Ⅲ complex

The bidentate phosphine oxide ligand 1,8-bis(diphenylphosphino) naphthalene oxide (NAPO) and its EuⅢ complex 1 Eu(TTA)3(NAPO) (TTA=2-thenoyltrifluoroacetonate) were chosen to study the effect of bidentate phosphine oxide ligand on the photophysical properties of the corresponding complex. The intramolecular energy transfer processes of 1 were studied. The investigation showed that with bidentate structure NAPO could suppress solvent-induced quenching by enforcing the ligand-ligand interaction and the rigidi...

钯催化辛烯烷氧基羰基化制备正壬酸甲酯研究

烷氧基羰基化反应是一步合成高价值酯类产品的重要方法,在精细化工领域有着重要的应用。但中长链烯烃反应速率较慢,工业生产应用时往往面临成本高、产物选择性差和催化剂易分解等难题。讨论了利用新型催化体系将内端或末端辛烯经烷氧基羰基化反应转化为正壬酸甲酯类化合物,分别探究了膦配体、催化剂、温度、压力、醇类和不同烯烃对辛烯烷氧基羰基化反应的影响,并结合分析结果阐释了辛烯烷氧基羰基化的反应机理。结果表明,在反应体系中引入含有二茂铁骨架的不对称双膦配体(L8)具有较好的催化活性和产物选择性,在最优反应条件(130℃、4 MPa、0.1 mol 1-辛烯、5.0 mmol对甲苯磺酸、0.1 mmol Pd(acac)2和0.3 mmol膦配体L8反应15 h)下表现出最优活性,此时1-辛烯转化率、壬酸甲酯产率和正壬酸甲酯与异壬酸甲酯物质的量比分别为99%、99%和17.2。与其他膦配体相比,膦配体L8中的二茂铁基团具有独特的电子性质,可以通过调节电子云密度影响膦配体的电子效应,从而优化金属中心的电子状态,提高催化剂的活性和产物选择性。此外,二茂铁骨架的刚性有助于配体在配位过程中保持特定的空间位阻,从而提高中长链烯烃烷氧基羰基化的产物选择性。

Investigation on the Coordination Mode of IL-Supported Diols Used as Phosphine-Free Ligands for Palladium Catalyzed Heck Reaction

The coordination mode of IL-supported diols used as phosphine-free ligands for palladium catalyzed Heck reaction has been investigated by tuning their compositions. The difference in coordination of these IL-supported diols with metal Pd in Heck reaction was related to the changes of the cation rings, leading to the different activities of Pd catalyst in the reaction. The experimental results indicated that the activities of Pd catalyst were affected mainly by n-electron density of the cation rings. Compared to pyridinium and piperidinium cations, imidazolium cations showed the best coordination to metal Pd. In the meantime, C-2 hydrogen and the length of alkyl side chains had impacts on the coordination as well.

笼状银配合物的合成及光催化应用

以水杨醛、溴乙胺氢溴酸盐、1-正丁基咪唑为原料合成配体SN-Br,利用溶剂热法合成笼状银配合物[Ag_(4)(PPh_(3))4Br_(4)].利用X-射线单晶衍射、能谱、热重等分析方法对目标配合物进行了表征.结构分析表明:目标配合物属于正交晶系,空间群为Pcnb,晶胞参数a=18.208 nm,b=18.490 nm,c=21.117 nm,α=β=γ=90°,V=7109.37 nm_(3),Z=24,4个Ag原子和4个三重桥联的Br原子交错排布,每个Ag原子与3个Br原子配位,进一步与膦配体配位形成笼状结构.对[Ag_(4)(PPh_(3))4Br_(4)]配合物进行光催化性能测试,发现其在紫外光照射下对甲基橙溶液的降解效果良好,降解率为96.8%.

SYNTHESES AND MOLECULAR STRUCTURES OF THE ASYMMETRICAL DIPHOSPHINE LIGANDS AND THEIR Pt, Ni ORGANOMETALLIC COMPLEXES

In this paper, we report a novel two-step synthetic method of the symmetrical and asymmetrical diphosphine ligands 1, 2-bis(ditertbutylphosphino)ethane and 1, 2-bis(phenyltertbutylphosphino) ethane, and simultaneously establish a novel synthetic method of diphosphine ligand 1, 4-bis(phosphinocyclopentyl)butane with larger chelate ring. The former was prepared from the reaction of 1, 2-bis(dichlorophosphino)ethane with Grignard reagent andalkyl lithium, respectively, the latter from the reaction of 1, 4-di-Grignard reagent with PCl_3. Furthermore, a series of organometallic complexes of Pt, Ni containing diphosphine chelate ligand were prepared from the reaction of (COD) PtCl_2 complex with diphosphine. These complexes are very stable. Among these complexes, the molecular structures of (d(t-Bu)pe)-PtCl_2, (dPCypb)PtCl_2 and ((n-Bu) (PCyp))_2PtCl_2 complexes have been determined by X-ray diffraction method indicating they are novel complexes. The influence of diphosphine ligand on the molecular structure of organotransition metal complexes is discussed.

Ir-Catalyzed Enantioselective Hydrogenation of 2H-1,4-Benzoxazines with a Chiral 1,2,3,4- Tetrahydro-l-naphthylamine Derived Phosphine-aminophosphine Ligand

Unsymmetrical hybrid chiral phosphine-aminophosphine ligand derived from 1,2,3,4-tetrahydro-l-naphthyl- amine has been found to be highly efficient in the Ir-catalyzed asymmetric hydrogenation of various 3-aryl-2H-1,4-benzoxazines, providing good enantioselectivities （up to 95% ee） and high catalytic activity （S/C up to 5000）.

Synthetic and structural chemistry of nickel(Ⅱ) complexes containing dithiolato and phosphine ligands Ⅰ. Preparation and crystal structure of Ni_2(PPh_3)_2(edt)_2

A nickel(Ⅱ) complex containing both dithiolato and phosphine ligands, Ni_2(PPh_3)_2(edt)_2 (edt = SCH_2CH_2S^(2-)), has been prepared and characterized by X-ray diffration. The complex crystallizes in the triclinic system, space group P-1, with a = 10.693(3), b = 17.457 (6), c = 10.606 (3)A, α= 102.84(2), β = 96.49 (2), γ = 82.56(3)°; V = 1906.8 A^3; D_c = 1.439g.cm^(-3) for Z=2; the final con- ventional R was 0.052 based on 3338 observed reflections. Nickel atoms are linked by two sulfur atoms from two edt ligands with the Ni--Ni distance of 2.893 A, and each Ni atom is coordinated by one phosphorus atom and three sulfur atoms with a square-planar geometry, where the average: length of Ni--S bond is 2.180 A and Ni--P bond 2.188 A. The UV-Vis and ~1H NMR spectra have also been recorded.

水溶性铑膦配合物催化烯烃氢甲酰化反应研究进展

水/有机两相体系中水溶性铑膦配合物催化的烯烃氢甲酰化反应由于具有环境友好和催化剂容易分离等优点而受到广泛关注.其中水溶性催化剂体系已经用于丙烯氢甲酰化反应制备丁醛的工业化生产.然而,长链烯烃在含有催化剂的水相中溶解性较差,反应速率较慢.综述了有关加速水/有机两相体系中长链烯烃氢甲酰化反应的方法和进展,包括使用具有表面活性的膦配体,以及在催化体系中添加环糊精和表面活性剂等促进剂.另外,还讨论了有关内烯烃氢甲酰化反应和提高直链醛选择性的方法.

膦氮配体半茂钛体系催化乙烯均聚合及乙烯与丙烯共聚合

合成了两种配合物中含有膦、氮的半茂钛催化剂，研究了甲基铝氧烷、四（五氟苯基）硼酸盐为助催化剂，不同n（Al）∶n（Ti）对乙烯均聚合及聚合物相对分子质量及其分布的影响。研究了催化剂用量、原料配比、反应压力、反应时间对乙烯与丙烯共聚合及共聚物组成、相对分子质量及其分布的影响。结果表明：合成的膦氮配体半茂催化剂可有效催化乙烯均聚合，在常压下，聚合活性可达0.62×106g/（mol·h），也可以有效催化乙烯与丙烯共聚合，与高活性茂金属催化剂催化效率相近；用该催化剂制备的高相对分子质量乙丙共聚物的相对分子质量分布窄，符合单活性中心催化剂的特点；共聚物的序列结构研究表明，乙烯与丙烯竞聚率之积接近1，共聚物无规性好。