(2,5-bis-diphenylphosphino)thiophene | 109828-60-6

• 物质功能分类: 医药中间体 - 杂环化合物 - 噻吩类化合物
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩类
• 英文名称: (2,5-bis-diphenylphosphino)thiophene
• 英文别名: Phosphine, 2,5-thiophenediylbis[diphenyl-；(5-diphenylphosphanylthiophen-2-yl)-diphenylphosphane
• CAS: 109828-60-6
• 化学式: C₂₈H₂₂P₂S
• 分子量: 452.496
• InChiKey: SFXMOXUVUAEIOF-UHFFFAOYSA-N

物化性质

• 沸点：
  554.0±35.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.6
• 重原子数：
  31
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  28.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (2,5-bis-diphenylphosphino)thiophene 在 双氧水 作用下， 以 氯仿 、 丙酮 为溶剂， 反应 1.0h， 以75%的产率得到2,5-bis(diphenylphosphine oxide)thiophene
  参考文献：
  名称：

  Spectroscopic Study of Phosphine-Substituted Oligothiophenes

  摘要：

  The spectroscopic behaviour (solution and solid-state absorption and emission) of a series of mono(diphenylphosphino) and bis-(diphenylphosphino) alpha-substituted oligothiophenes varying in length from one to three thienyl rings is described. The absorption spectra red-shift with increasing oligomer length, and the spectra of the bisphosphines are red-shifted, relative to the monophosphines that contain the same number of thienyl groups. In solution, emission from the mono- and bithienyl compounds is broad and shows a large Stokes shift, attributed to a planar excited state due to the n --> pi* nature of the excitation. Emission from the terthienyl compounds shows a much smaller Stokes shift and is attributed to a thienyl-based pi --> pi* transition. In the solid state, similar effects are observed in both absorption and emission spectra. Density functional theory (DFT) calculations show that the contribution of the P lone pair to the highest occupied molecular orbital (HOMO) diminishes as the oligomer length increases, supporting the experimental results.

  DOI：

  10.1021/jp047037g
• 作为产物：
  描述：

  苄基二苯膦 在 15-冠醚-5 、 sodium 作用下， 以 四氢呋喃 为溶剂， 反应 17.0h， 生成 (2,5-bis-diphenylphosphino)thiophene
  参考文献：
  名称：

  通过钠选择性裂解C-P键从ArCl制备有机膦的方法

  摘要：

  研究了磷化钠R 2 PNa和其他碱金属磷化物R 2 PM（M = Li和K）的制备，应用和反应机理。R 2 PNa可以通过SD（精细分散在矿物油中的钠）与次膦酸酯R 2 POR'和氯膦R 2 PC1的反应准确而选择性地制备。R 2 PNa也可以通过选择性裂解C–P键由三芳基膦和二芳基膦制备。在这些反应中，Na优于Li和K。R 2 PNa与多种ArCl反应以有效产生R 2PAr。ArCl优于ArBr和ArI，因为它们只会降低产品收率。另外，Ph 2 PNa优于Ph 2 PLi和Ph 2 PK，因为Ph 2 PLi不产生与PhCl的偶联产物，而Ph 2 PK仅产生低产率的产物。ArCl苯环上的吸电子基团极大地促进了与R 2 PNa的反应，而烷基降低了反应活性。氯乙烯和烷基氯RC1也有效地反应。当t-BuCl没有产生相应的产物，金刚烷基卤化物可以高产率得到相应的膦。通过这种方法，由相应的氯化物制备了多种膦。还可以方便地从Ph

  DOI：

  10.1021/acs.organomet.0c00295

文献信息

• Group 8, 9 or 10 transition metal catalyst for olefin polymerization
  申请人：Nova Chemicals (International) S.A.

  公开号：US06339161B1

  公开（公告）日：2002-01-15

  Olefin co- or homopolymers having a good molecular weight and short chain branching may be prepared in the presence of a tridentate complex of a Group 8, 9 or 10 metal.

  具有良好分子量和短链支化的烯烃共聚物或同聚物可以在第8、9或10族金属的三牙配合物存在下制备。
• trans-bis(diphenylphosphine)cyclopropane; a ligand selective for binuclear complexation with ca. 4.5 Å intermetallic separation
  作者：John M. Brown、Andrew R. Lucy

  DOI：10.1016/0022-328x(86)80367-9

  日期：1986.10

  )cyclopropane in 56% overall yield. The new ligand was found to have a strong affinity for AgBF4 forming a 2/2 complex under conditions where related ligands gave a mixture of 2/2 and 3/2 adducts. This complex could be employed as precursor to a cationic binuclear rhodium carbonyl complex P2RH2+(CO)3Cl. When synthesis of the coresponding iridium complex was attempted, a soluble yellow adduct of P2Ir2(CO)2Cl2

  用（CH 3）2 S（CH 2）在二甲亚砜中处理反式-1,2-双（二苯基膦酰基）乙烯，并用HSiCl 3还原产物，得到反式-双（二苯基膦基）环丙烷，总产率为56％。发现新的配体在相关配体产生2/2和3/2加合物的混合物的条件下对形成2/2复合物的AgBF 4具有很强的亲和力。该络合物可用作阳离子双核羰基铑铑络合物P 2 RH 2 +（CO）3 Cl的前体。尝试合成相应的铱配合物时，P 2的可溶性黄色加合物得到Ir 2（CO）2 Cl 2和AgBF 4，假定其含有Ir 3 Ag 3 Ir键。
• Synthesis, Characterization and Quantum Mechanical Calculations of [Au ₁₈ Se ₈ (dppthph) ₆ ]Cl ₂
  作者：Paloma Sevillano、Olaf Fuhr、Oliver Hampe、Sergej Lebedkin、Christian Neiss、Reinhart Ahlrichs、Dieter Fenske、Manfred M. Kappes

  DOI：10.1002/ejic.200700870

  日期：2007.11

  The reaction of [Au(tht)Cl] (tht = tetrahydrothiophene) with 2,5-bis(diphenylphophanyl)thiophene (dppthph) and Se(SiMe3)2 leads to the formation of [Au18Se8(dppthph)6]Cl2. This compound crystallizes in two modifications, both containing a cluster dication with nearly identical gold–selenium cores. The dication consists of two subunits only connected by six aurophilic interactions. ESI MS demonstrates

  [Au(tht)Cl]（tht = 四氢噻吩）与 2,5-双（二苯基膦基）噻吩（dppthph）和 Se(SiMe3)2 的反应导致形成 [Au18Se8(dppthph)6]Cl2。该化合物以两种变体结晶，均包含具有几乎相同的金-硒核的簇状标记。指示由两个亚基组成，仅通过六个嗜热相互作用连接。ESI MS 表明，即使在气态下，这些也能促进簇亚基的凝聚。SCS-MP2 计算表明，二聚体是一种可转移物质，最终通过库仑势垒阻止其解离。此外，光致发光测量表明，簇分子配体壳的微小差异导致两种修饰的不同光致发光特性。(© Wiley-VCH Verlag GmbH & Co. KGaA,
• Structural and Electronic Properties of Phosphino(oligothiophene) Gold(I) Complexes
  作者：Tracey L. Stott、Michael O. Wolf、Brian O. Patrick

  DOI：10.1021/ic0493200

  日期：2005.2.1

  A series of gold(I) complexes containing phosphino(oligothiophene) ligands of varying conjugation length has been prepared. Solid state crystal structures of (PT3)AuCl (PT3 = 5-diphenylphosphino-2,2':5',2"-terthiophene) and AuCl-(PTP)AuCl (PTP = 2,5-diphenylphosphinothiophene) have been obtained. The complex AuCl(PTP)AuCl crystallizes as a dimer with two intermolecular Au-Au contacts. Variable temperature NMR spectroscopy is used to demonstrate the presence of aurophilic interactions in solution for Aul(PTP)Aul. Dual emission is observed for AuCl(PTP)AuCl in solution and is attributed to emission from both monomer and dimer. In the solid state, dimer emission is dominant. The iodo analogue, Aul(PTP)Aul, shows only low energy dimer emission in both solution and the solid state. Compounds in which the ligands contain longer bridges (either bithienyl or terthienyl) show absorption and emission bands due to the pi-pi* transition only, both in solution and the solid state.
• Ready Approach to Organophosphines from ArCl via Selective Cleavage of C–P Bonds by Sodium
  作者：Jingjing Ye、Jian-Qiu Zhang、Yuta Saga、Shun-ya Onozawa、Shu Kobayashi、Kazuhiko Sato、Norihisa Fukaya、Li-Biao Han

  DOI：10.1021/acs.organomet.0c00295

  日期：2020.7.27

  mechanism of sodium phosphide R2PNa and other alkali metal phosphides R2PM (M = Li and K) have been studied. R2PNa could be prepared, accurately and selectively, via the reactions of SD (sodium finely dispersed in mineral oil) with phosphinites R2POR′ and chlorophosphines R2PCl. R2PNa could also be prepared from triarylphosphines and diarylphosphines via the selective cleavage of C–P bonds. Na was superior

  研究了磷化钠R 2 PNa和其他碱金属磷化物R 2 PM（M = Li和K）的制备，应用和反应机理。R 2 PNa可以通过SD（精细分散在矿物油中的钠）与次膦酸酯R 2 POR'和氯膦R 2 PC1的反应准确而选择性地制备。R 2 PNa也可以通过选择性裂解C–P键由三芳基膦和二芳基膦制备。在这些反应中，Na优于Li和K。R 2 PNa与多种ArCl反应以有效产生R 2PAr。ArCl优于ArBr和ArI，因为它们只会降低产品收率。另外，Ph 2 PNa优于Ph 2 PLi和Ph 2 PK，因为Ph 2 PLi不产生与PhCl的偶联产物，而Ph 2 PK仅产生低产率的产物。ArCl苯环上的吸电子基团极大地促进了与R 2 PNa的反应，而烷基降低了反应活性。氯乙烯和烷基氯RC1也有效地反应。当t-BuCl没有产生相应的产物，金刚烷基卤化物可以高产率得到相应的膦。通过这种方法，由相应的氯化物制备了多种膦。还可以方便地从Ph