Rh/Ph3PO催化剂体系的辛烯氢甲酰化反应性能考察和原位红外表征

考察了反应温度,ＣＯ／Ｈ２压力和Ｐ／Ｒｈ比等因素,对Ｒｈ／Ｐｈ３ＰＯ催化剂催化混合辛烷氢甲酰化反应活性的影响,优化出最佳反应条件,并采用加热加压的原位红外表征方法,跟踪了在１－辛烯反应中Ｒｈ／Ｐｈ３ＰＯ催化剂的活化、中间活性物种的产生和分解消失等瞬态变化情况。     

Regioselective synthesis of (E)-3-[2-(arylmethylene)-1-(arylsulfonyl)hydrazino]-2-propenoates via the reaction of arylsulfonyl hydrazones and alkyl propiolates in the presence of triphenylphosphine

A regioselective method for the synthesis of (E)-3-[2-(arylmethylene)-1-(arylsulfonyl)hydrazino]-2-propenoates is described. The reaction takes place between arylsulfonyl hydrazones and alkyl propiolates in the presence of triphenylphosphine as the catalyst.     

Four mono-/bi-nuclear palladium(II) complexes of triphenylphosphine and heterocyclic-N/NS ligands: Synthesis, structural characterization and luminescence properties

The reactions of palladium(II) chloride, PPh₃ and heterocyclic-N/NS ligand in a mixture of CH₃CN (5 ml) and CH₃OH (5 ml) produced [PdCl₂(PPh₃)(L1)]·(CH₃CN) (1) (L1 = ADMT = 3-amino-5,6-dimethyl-1,2,4-triazine), [PdCl₂(PPh₃)(L2)] (2) (L2 = 3-CNpy = 3-cyanopyridine), [PdCl(PPh₃)(L3)]₂·(CH₃CN) (3), [PdCl(PPh₃)₂(HL3)]Cl (4) (HL3 = Hmbt = 2-mercaptobenzothiazole). The coordination geometry around the Pd atoms in these complexes is a distorted square plane. In 3, L3 acts as a bidentate ligand, bridging two metal centers, while in 4, HL3 appears as monodentate ligand with one nitrogen donor atom uncoordinated. Complexes 1-4 are characterized by IR, luminescence, NMR and single crystal X-ray diffraction analysis. All complexes exhibit luminescence in solid state at room temperature.     

钴膦基元化合物的电化学行为

近年来，随着硫、脚混配配位化学的迅猛发展，有机卿参与的过渡金属流基化合物正在受到越来越多的重视［‘，’］．有机磷的参与增加了金属硫基配合物的多样性，推动了金属流基配位体系的合成化学和结构化学的发展．Co（PPh3hCI。和Co（PPha）aCI（PPh。为三苯基磷）是重要的含     

Palladium(II) and palladium(0)-cocatalyzed ring opening and oxidation reactions of 2-(arylmethylene)cyclopropylcarbinols

In the presence of Pd(II) acetate and triethylamine as well as triphenylphosphine, 2-(arylmethylene)cyclopropylcarbinols 1 underwent ring opening and oxidation reactions smoothly to deliver (2E,4E)-5-arylpenta-2,4-dienals 2 in toluene at 60 °C in moderate to good yields under ambient atmosphere. Mechanisms involved with an in situ generated Pd(0) species from Pd(II) and Et₃N or PPh₃ catalyzed isomerization of 1 to provide (E,E)-5-arylpenta-2,4-dien-1-ols 3 and following a Pd(II) catalyzed aerobic oxidation of 3 have been proposed on the basis of control and deuterium labeling experiments.     

A chemoselective and one-pot synthesis of 5-hydroxy and 7-hydroxy coumarin derivatives

Abstract  An efficient one-pot reaction of dialkyl acetylenedicarboxylates with 2,4-dihydroxybenzo(or aceto)phenones in the presence of triphenylphosphine produces 5-hydroxy- and 7-hydroxycoumarin derivatives. The novel procedure features short reaction time, fairly good yields, and simple workup. Graphical abstract        

环钯化二茂铁亚胺-三苯基膦配合物的合成、表征及催化Suzuki反应研究

为筛选高效催化Suzuki反应的催化剂, 合成了3种新的环钯化二茂铁亚胺-三苯基膦配合物2~4, 经元素分析(或HRMS)、 红外光谱和核磁共振谱对其结构进行了表征, 并通过X射线单晶衍射测定了化合物3的晶体结构. 这些化合物容易合成, 在空气和溶液中稳定, 可用作芳基溴及杂芳基溴与苯基硼酸偶联的Suzuki反应催化剂. 使用摩尔分数为0.01%的催化剂3, 以2倍量的K3PO4为碱, 于110 ℃下, 在甲苯中反应5~15 h, 使具有不同电子和位阻效应的取代芳基溴及杂芳基溴能以较高的产率与苯基硼酸反应生成偶联产物; 与溴苯相比, 带吸电子基的溴苯反应活性较高, 催化剂的摩尔分数降低至0.001%时, 仍能得到较高产率, 而带强给电子基的溴苯如4-溴苯甲醚及带邻位取代基的溴苯在其它条件相同时, 需要延长反应时间才能得到较高的产率.     

One‐Step Synthesis of Dialkyl 2‐[(4‐Methylphenyl)sulfonyl]‐1H‐pyrrole‐3,4‐dicarboxylates by Reaction of Acetylenedicarboxylates with ‘Tosylmethyl Isocyanide’ (TsMIC) and Triphenylphosphine

The reactive 1 : 1 adducts in the reaction between Ph₃P and dialkyl acetylenedicarboxylates have been trapped with ‘tosylmethyl isocyanide’ (TsMIC ; 1 ) to yield dialkyl 2‐[(4‐methylphenyl)sulfonyl]‐1H‐pyrrole‐3,4‐dicarboxylates 3 (Scheme 1). The structures of the highly functionalized compounds 3 were corroborated spectroscopically (IR, ¹H‐ and ¹³C‐NMR, and EI‐MS) and by elemental analyses. A plausible mechanism for this type of cyclization is proposed (Scheme 2).     

Efficient Synthesis of Dialkyl (2Z)‐2‐[(E)‐1‐Aryl‐2‐(3‐arylquinoxalin‐2‐yl)ethenyl]but‐2‐enedioates

The reaction of dialkyl acetylenedicarboxylates 4 with 1‐aryl‐2‐[(3‐arylquinoxalin‐2(1H)‐ylidene)ethanones 3 in the presence of Ph₃P leads to dialkyl (2Z)‐2‐[(E)‐1‐aryl‐2‐(3‐arylquinoxalin‐2‐yl)ethenyl]but‐2‐enedioates 1 in good yields.     

Variable Bonding Modes of Pyrimidine‐2‐thione in PdII/PtII Complexes [M(η2‐N,S‐pymS)(η1‐S‐pymS)(PPh3)] and [M(η1‐S‐pymS)2(L‐L)] (L‐L = dppm,dppe)

Reactions of pyrimidine‐2‐thione (HpymS) with Pd^II/Pt^IV salts in the presence of triphenyl phosphine and bis(diphenylphosphino)alkanes, Ph₂P‐(CH₂)_m‐PPh₂ (m = 1, 2) have yielded two types of complexes, viz. a) [M(η²‐N, S‐ pymS)(η¹‐S‐ pymS)(PPh₃)] (M = Pd, 1 ; Pt, 2 ), and (b) [M(η¹‐S‐pymS)₂(L‐L)] {L‐L, M = dppm (m = 1) Pd, 3 ; Pt, 4 ; dppe (m = 2), Pd, 5 ; Pt, 6 }. Complexes have been characterized by elemental analysis (C, H, N), NMR spectroscopy (¹H, ¹³C, ³¹P), and single crystal X‐ray crystallography ( 1 , 2 , 4 , and 5 ). Complexes 1 and 2 have terminal η¹‐S and chelating η²‐N, S‐modes of pymS⁻, while other Pd/Pt complexes have only terminal η¹‐S modes. The solution state ³¹P NMR spectral data reveal dynamic equilibrium for the complexes 3 , 5 and 6 , whereas the complexes 1 , 2 and 4 are static in solution state.