2-Diphenylphosphanylpropanenitrile | 1579211-45-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-Diphenylphosphanylpropanenitrile
• CAS: 1579211-45-2
• 化学式: C₁₅H₁₄NP
• 分子量: 239.257
• InChiKey: VRAPHHNYWNLQDM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  丙烯腈 、 二苯基膦 在 C₂₂H₃₀CaN₄S₃Si₂ 作用下， 以 氘代苯 为溶剂， 反应 1.0h， 以5%的产率得到2-Diphenylphosphanylpropanenitrile
  参考文献：
  名称：

  第 2 组与硫代吡啶基蝎配体配合物的合成、表征和反应性

  摘要：

  在这里，我们报告了前配体三（2-吡啶硫基）甲烷（HTptm）与各种碱土（AE）试剂的反应性：（1）二烷基镁试剂和（2）AE双酰胺（AE = Mg-Ba）。通式 [Mg(Tptm)(R)] (R = Me, n Bu; Tptm = {C(S–C 5 H 4 N) 3 } - ) 和 [AE(Tptm)(N′′) 的杂配配合物] (AE = Mg–Ba; N′′ = {N(SiMe 3 ) 2 } - ) 是 HTptm 与 R 2 Mg 或 [AE(N′′) 2 ] 2反应的目标。前配体与二烷基镁试剂的反应导致形成 [{Mg(κ 3 C , N ,N –C{Bu}{S–C 5 H 4 N} 2 )(μ-S–C 5 H 4 N)} 2 ] ( 1 ) 和 [{Mg(κ 3 C , N , N –C{Me }{S-C 5 H 4 N} 2 )(μ-OSiMe 3 )} 2 ] ( 2 ) 分别是烷基转移到甲烷化物碳上并伴随

  DOI：

  10.1039/d2dt02012b

文献信息

• Hydrophosphination of Activated Alkenes by a Cobalt(I) Pincer Complex
  作者：Roberto Nolla‐Saltiel、Ana M. Geer、Laurence J. Taylor、Olivia Churchill、E. Stephen Davies、William Lewis、Alexander J. Blake、Deborah L. Kays

  DOI：10.1002/adsc.202000514

  日期：2020.8.4

  Herein we report the synthesis of three heteroleptic first‐row transition metal(II) complexes containing carbazolido NNN pincer ligands and conversion to the corresponding metal(I)‐carbonyl complexes via a reductive carbonylation route. These complexes are precatalysts for the hydrophosphination of activated alkenes, affording a cobalt‐catalysed hydrophosphination process that solely and selectively

  在本文中，我们报告了三种含咔唑NNN钳形配体的第一排过渡金属（II）杂合剂的合成，并通过还原羰基化途径转化为相应的金属（I）-羰基配合物。这些络合物是活化烯烃进行加氢磷酸化的预催化剂，提供了钴催化的加氢磷酸化过程，该过程仅可选择性地产生β加成（抗马尔科夫尼科夫）产物。已经使用多种活化的烯烃研究了这种转化的范围。底物配位中间体的分离和表征揭示了可用的配位点，可提供对拟议催化循环的深入了解。
• Visible Light Photocatalysis Using a Commercially Available Iron Compound
  作者：Justin K. Pagano、Christine A. Bange、Sarah E. Farmiloe、Rory Waterman

  DOI：10.1021/acs.organomet.7b00499

  日期：2017.10.23

  reactivity over the same transformations using 1 or related CpFeMe(CO)2 under UV irradiation, consistent with the notion that hydrophosphination with 1 proceeds via formation of CpFe(CO)2•. These results demonstrate that catalyst selection can avail the use of commercially available LED bulbs as photon sources, potentially replacing mercury arc lamps or other energy intensive processes in known or new catalytic

  [CPFe的量（CO）2 ] 2（1）（CP =η 5 -C 5 H ^ 5）是一种有效的预催化剂用于烯烃的Ph的hydrophosphination 2可见光的照射下，这似乎是，以促进金属的独特方式下PH -催化的磷酸化。另外，1是用于胺硼烷脱氢和由叔硅烷形成硅氧烷的光催化剂。这些反应具有相似的，如果没有得到改善，并且使用了相同的变换反应1或相关CPFeMe（CO）2紫外光照射下，与概念相一致，即与hydrophosphination 1通过形成CPFe（CO）2 •进行。这些结果表明，催化剂的选择可以利用市售的LED灯泡作为光子源，在已知的或新的催化反应中可能替代汞弧灯或其他耗能大的过程。
• POLYCARBONATE RESIN COMPOSITION, MOLDED ARTICLE, AND STRUCTURAL MEMBER FOR SOLAR POWER GENERATION
  申请人：Idemitsu Kosan Co., Ltd

  公开号：EP3275936A1

  公开（公告）日：2018-01-31

  Provided are a polycarbonate resin composition, a molded article, and a structure member for solar photovoltaic power generation, the polycarbonate resin composition including: (A) 100 parts by mass of a resin mixture formed of 30 mass% to 100 mass% of a polycarbonate-polyorganosiloxane copolymer (A-1) having a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II), and having an average chain length n of a polyorganosiloxane moiety of from 70 to 500, and 70 mass% to 0 mass% of an aromatic polycarbonate resin (A-2) except the polycarbonate-polyorganosiloxane copolymer (A-1); (B) 0.08 part by mass to 0.3 part by mass of a silsesquioxane; (C) 0.05 part by mass to 0.2 part by mass of an alkaline metal salt and/or an alkaline earth metal salt of an organic sulfonic acid; (D) 0 parts by mass to 0.3 part by mass of a polytetrafluoroethylene having a fibril-forming ability; (E) 1 part by mass to 10 parts by mass of titanium dioxide; and (F) 0.1 part by mass to 3 parts by mass of carbon black.

  本发明提供了一种用于太阳能光伏发电的聚碳酸酯树脂组合物、模塑制品和结构构件，该聚碳酸酯树脂组合物包括：(A) 100质量份的树脂混合物，该混合物由30质量％至100质量％的聚碳酸酯-聚有机硅氧烷共聚物（A-1）形成，该共聚物具有通式（I）代表的重复单元和通式（II）代表的重复单元，且聚有机硅氧烷分子的平均链长n为70至500，以及除聚碳酸酯-聚有机硅氧烷共聚物（A-1）之外的70质量％至0质量％的芳香族聚碳酸酯树脂（A-2）；(B) 0.08质量份至0.3质量份的硅倍半氧烷；(C) 0.05质量份至0.2质量份的有机磺酸的碱金属盐和/或碱土金属盐；(D) 0质量份至0.3质量份的具有纤维形成能力的聚四氟乙烯；(E) 1质量份至10质量份的二氧化钛；以及(F) 0.1质量份至3质量份的炭黑。
• Reactivity of Ruthenium Phosphido Species Generated through the Deprotonation of a Tripodal Phosphine Ligand and Implications for Hydrophosphination
  作者：Peter E. Sues、Alan J. Lough、Robert H. Morris

  DOI：10.1021/ja5006724

  日期：2014.3.26

  The fragmentation of the 1,1,2-tris(diphenylphosphino)ethane ligand in [RuCp*((Ph2P)(2)CHCH2PPh2)][PF6] (1) was explored through treatment with base under aprotic conditions. The neutral phosphido complex RuCp*(PPh2CH=CHPPh2) (PPh2) (2) with a (Z)-1,2-bis(diphenylphosphino)ethene (dppen) ligand was generated through a base-facilitated dehydrophosphination reaction. Installation of a bis(p-tolyl)phosphido ligand was attempted by combining bis(p-tolyl)phosphine with RuCp*(dppen)Cl in the presence of KOtBu, but surprisingly, the unsymmetrical diphenylphosphido compound RuCp*(Ph2PCHCHP-(p-tol)(2))(PPh2) (5) was generated instead. The ligand rearrangement reaction was driven by the greater electron density on the bis(p-tolyl)phosphido moiety. Density functional theory calculations showed that fragmentation to the 1,2-disubstituted ligand was thermodynamically favored over the 1,1-disubstituted ligand and that intramolecular phosphido exchange was kinetically accessible at room temperature. The greater basicity of the bis(p-tolyl)phosphido ligand was experimentally verified by the measured pK(a)(THF) of 28 for the acid/base pair [RuCp*(Ph2P(o-C6H2OPPh2)(P(p-tolyl)(2)H)](+)/RuCp*(Ph2P(o-C6H4)PPh2)(P(p-tolyl)(2)) versus 25 for the acid/base pair [RuCp*(Ph2P(o-C6H4)PPh2)(PPh2H)]+/RuCp*(Ph2P(o-C6H4)PPh2)(PPh2) (7). For comparison, the approximate pK(a)(THF) values for free P(p-tolyl)(2)H/[K(crypt)]P(p-tolyl)(2) and free PPh2H/[K(crypt)]PPh2 are 43 and 38, respectively. This is the first quantitative measurement of the large effect that coordination to a metal center, in this case ruthenium(II), has on the acidity of secondary phosphines. This is useful information for designing and understanding hydrophosphination catalysts. Complexes 2 and 7 are catalysts for the addition of PPh2H to acrylonitrile, but they deactivate fairly rapidly. The pK(a)(THF) measurements are consistent with a catalytic cycle involving a Michael addition step. Complex 2 in solution underwent a slow, unprecedented rearrangement of P C, C C, and C H bonds to give crystalline Ru(C-5(CH3)(4)(CH2C6H5))(Ph2PCH2CH2PPh(o-C6H4)PPh) (9) in high yields, demonstrating the unpredictable reactivity of phosphido ligands.
• Inner- and Outer-Sphere Roles of Ruthenium Phosphido Complexes in the Hydrophosphination of Alkenes
  作者：Roman G. Belli、Krista M. E. Burton、Stephanie A. Rufh、Robert McDonald、Lisa Rosenberg

  DOI：10.1021/acs.organomet.5b00835

  日期：2015.12.14

  An inner-sphere synthetic cycle for the hydrophosphination of alkenes is proposed, based on observed [2 + 2] cydoaddition of a wide range of alkenes at a coordinatively unsaturated Ru=PR2 complex. Key intermediates in the cycle were prepared, and their reactions with various organic acid/base pairs were examined to identify both new ruthenium precursors and base cocatalysts that allow turnover of the proposed cycle. Two new cationic ruthenium indenyl phosphine complexes were isolated and structurally characterized. Although preliminary screening studies show the moderate activity of these and related neutral phosphido complexes for catalytic hydrophosphination of acrylonitrile by both HPPh2 and HPCy2, and comparable activity for the hydrophosphination of tert-butyl acrylate by HPPh2, no activity was observed for the analogous hydrophosphination of 1-hexene. This is attributed to strong binding of the substrate phosphine to the unsaturated, planar Ru=PR2 fragment generated in situ, which inhibits the innersphere, alkene cydoaddition mechanism. An alternative, outer-sphere Michael addition process, involving a saturated complex with a strongly nudeophilic pyramidal Ru-PR2 ligand, is proposed to rationalize the observed selectivity for catalytic hydrophosphination of activated, but not simple, alkenes. Implications for further catalyst development are discussed.