2-(diphenylphosphino)methyl-6-methylpyridine | 60398-58-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 2-(diphenylphosphino)methyl-6-methylpyridine
• 英文别名: 2-(Diphenylphosphinomethyl)-6-methylpyridine；(6-methylpyridin-2-yl)methyl-diphenylphosphane
• CAS: 60398-58-5
• 化学式: C₁₉H₁₈NP
• 分子量: 291.332
• InChiKey: WXIYKCFXQJFFPK-UHFFFAOYSA-N

物化性质

• 沸点：
  413.5±33.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-(diphenylphosphino)methyl-6-methylpyridine 在 正丁基锂 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 41.0h， 生成 [MoCl₃(2-(di-tert-butylphosphino)methyl-6-(diphenylphosphino)methylpyridine)]
  参考文献：
  名称：

  Synthesis and Catalytic Activity of Molybdenum–Dinitrogen Complexes Bearing Unsymmetric PNP-Type Pincer Ligands

  摘要：

  Novel dinitrogen-bridged dimolybdenum complexes bearing unsymmetric PNP-type pincer ligands are prepared and characterized by X-ray analysis. A molybdenum-dinitrogen complex bearing 2-(di-1-adamantylphosphino)methyl-6-(di-tert-butylphosphino)methylpyridine has been found to work as an effective catalyst toward the formation of ammonia from molecular dinitrogen under ambient conditions.

  DOI：

  10.1021/om301046t

文献信息

• 2-[(Diphenylphosphino)methyl]-6-methylpyridine (PN) coordination chemistry at triosmium clusters: Regiospecific ligand activation and DFT evaluation of the isomeric Os3(CO)10(PN) clusters
  作者：Chen-Hao Lin、Vladimir N. Nesterov、Michael G. Richmond

  DOI：10.1016/j.jorganchem.2013.03.048

  日期：2013.11

  hydride HOs3(CO)9[μ-CH2(NC5H3)CH2PPh2]. The PN ligand in 7 undergoes P–C bond activation in toluene at 110 °C to afford the 50e cluster Os3(CO)9(μ-C6H4)(μ-PPh) (9), which contains face-capping benzyne and phosphinidene moieties. The bonding between the benzyne moiety and the opened Os3 frame in 9 has been examined computationally, and these data are discussed relative to σ and π bonding contributions

  2-[（（二苯基膦基）甲基] -6-甲基吡啶（PN）与Os 3（CO）12- n（MeCN）n的反应[ n  = 0（1），1（2），2（3）]已被调查。OS 3（CO）12在我的存在下用PN发生反应3 NO，得到簇OS 3（CO）11（κ 1 -PN）（4）和1,2- OS 3（CO）10（κ 1 - PN）2（5）。X射线衍射分析证实了4和5中的膦的赤道配位，后一簇中的两个膦相对于包含两个配体的Os-Os载体表现出1,2-反式取向。所述的治疗的MeCN取代簇锇3（CO）11（MeCN中）和PN（1：1倍的比例）的CH 2氯2给出簇4和5中，除了的HO 3（η 1 -Cl）（CO）10（κ 1 -PN）（6）作为反应溶剂的竞争性激活的结果。集群6含有48e，并且衍射结构揭示了位于相邻原子上的轴向氯化物和赤道膦配体的存在。6个桥联氢化物配体跨越Cl，P-取代的Os-Os载体。O的反应3（C
• New Insight into the Reactivity of Pyridine-Functionalized Phosphine Complexes of Ruthenium(II) with Respect to Olefin Metathesis and Transfer Hydrogenation
  作者：Emmanuelle Mothes、Stephane Sentets、Maria Asuncion Luquin、René Mathieu、Noël Lugan、Guy Lavigne

  DOI：10.1021/om7012106

  日期：2008.3.24

  norbornene in the presence of trimethylsilyldiazomethane as the carbene source. The same compounds 4nx are also used as catalyst precursors in the transfer hydrogenation of a series of ketone substrates using alcohol as the hydrogen source. For example, the hydrogenation of cyclohexanone is achieved in 99% yield within 45 s with only 0.01 mol (0.1 mol %) of the precatalyst RuCl2(Ph2PCH2pic)(PPh3)-trans-Cl (41a)

  本文研究了Ru（II）的一系列吡啶官能化膦配合物RuCl 2（L nx）（PPh 3）（L nx = R 2 PCH 2（C 5 H 2 R'R''N）），在不同的磷在取代基的性质（上标标签ñ在大号NX定义为ñ = 1为R = PH，ñ = 2 R = CY）和/或吡啶基组（上标标签X在大号NX定义为X =一个为吡啶甲基，注意到PIC，和X = b为喹啉基，五重峰指出）和公开它们的反应性的新的方面相对于催化。配体2-[（（二苯基膦基）甲基] -6-甲基吡啶，L 1a，2-[（（二苯基膦基）甲基]喹啉，L 1b，2-[（（二环己基膦基）甲基] -6-甲基吡啶，L 2a和2-制备[（二环己基膦基）甲基]喹啉，L 2b，并在优化的实验条件下分别使其与RuCl 2（PPh 3）3反应。在初步测试中，RuCl 2（PPh 3）3与L 1a的化学计量比为1/1的金属/配体比率得到三个络合物，即[RuCl
• Selective Carbanion–Pyridine Coordination of a Reactive P,N Ligand to Rh ^I
  作者：Marc Devillard、Andreas Ehlers、Maxime A. Siegler、Jarl Ivar van der Vlugt

  DOI：10.1002/chem.201805504

  日期：2019.3.12

  κ2‐C,N‐κ1‐P ligand with a carbanionic methine carbon atom directly bound to rhodium as part of a four‐membered Rh‐N‐C‐C rhodacycle. This dimer undergoes meta‐pyridine C−H activation facilitated by weak bases, which leads to a desymmetrization of the system and provides a σ,π‐bridging 3‐pyridyl fragment bound to RhI. The facile Si−C cleavage strategy may pave the way to studying the reactivity and functionalization

  金属中心外围具有活性碳位点的配体已成为激活金属-配体键的有效方法。这些活性碳位点通常是通过去质子化策略产生的。碳硅键断裂是获得此类结构的潜在替代方案。在此，公开了在 [Rh I (Cl)(CO)( PN Si2 )] ( 1 )配位层中双甲硅烷基取代的P , N支架PN Si2与叠氮化钠的单脱甲硅烷基化。这提供了一种独特的双核阴离子 κ 2 -C 、N -κ 1 -P配体，其碳负离子次甲基碳原子直接与铑结合，作为四元 Rh-N-C-C 铑环的一部分。该二聚体在弱碱的促进下经历间吡啶 CH 活化，导致系统去对称化并提供与 Rh I结合的 σ,π 桥接 3-吡啶基片段。简便的 Si−C 裂解策略可能为研究用于选择性转化的各种 κ 2 ‐ C、N配位吡啶支架的反应性和功能化铺平道路。
• A metal alkynyl molecular wire with PN ligands: Synthesis, isomerization, physical properties and single-molecule conductance
  作者：Yuya Tanaka、Aki Okamoto、Shintaro Fujii、Tomoaki Nishino、Munetaka Akita

  DOI：10.1016/j.ica.2022.121211

  日期：2023.1

  electronic structures of 1 and 2 with the HOMOs being close to the Fermi energy level of gold electrodes. STM-break junction measurements of Au-syn-1-Au (Au: gold electrode) revealed high single-molecule conductance (1.9 × 10–2 G0), which is comparable to that of Au-2-Au. Calculations on the basis of the DFT-non equilibrium Green’s function method also support the experimental results. Notably, the molecular

  作为有机金属分子线的新候选者，我们设计了一种钌反式-二（炔基）分子线1 H , trans -Ru(PN) 2 (C≡CC≡CH) 2，具有两种混合的膦-吡啶支持配体（PN ：2-二苯基膦甲基-6-甲基吡啶）。虽然具有顺式和反构型的两种立体异构体是可能的，但三异丙基甲硅烷基丁二炔基前体syn - 1 TIPS和syn - 1 H的顺式异构体是以直接和立体选择性的方式制备的。电化学分析syn - 1 TIPS揭示了一个几乎可逆的氧化还原波，与双（二膦）类似物2 TMS、反式-Ru(dppe) 2 (C≡CC≡C-SiMe 3 ) 2相比，其电位发生阴极偏移。密度泛函理论 (DFT) 研究支持1和2的电子结构的相似性， HOMO 接近金电极的费米能级。Au -syn -1 - Au ( Au _：金电极）显示出高单分子电导（1.9 × 10 –2 G 0），与Au - 2 - Au相当。基于D
• Study of the Bonding Properties of the New Ligands C₅H₃N(2-R‘)(6-CH₂PPhR) toward Rhodium(I). Evidence for a Dynamic Competition for Bonding between O- and N-Donor Centers When R = <i>o</i>-Anisyl, R‘ = Me
  作者：Hong Yang、Noël Lugan、René Mathieu

  DOI：10.1021/om960982+

  日期：1997.5.1

  The bonding properties of the optically active chiral-at-P polydentate ligands C5H3N(2-R')(6-CH2PPhR) (R = Me, R' = H, Me; R o-anisyl, R' = H, Me) and the achiral ligand C5H3N(2-Me)(6-CH2PPh2) toward (COD)Rh+ are reported. The results show that steric hindrance of the 2-position of the pyridyl ring induces a labile character of the Rh-N bond. Moreover, for R = o-anisyl and R' = Me, a dynamic competition for bonding between the N-and O-donating centers is observed. Comparison of the solid state structures of complexes [Rh(COD)(C5H4N(2-CH2PPhMe)][BF4] and [Rh(COD)(C5H3N(2-Me)(6-CH2PPh2)][BF4] shows a significant bond lengthening of the Rh-N bond in the latter complex, consistent with its fluxional behavior observed in solution.