(1,3,5-(CH3)3-2,6-(iPr2PCH2)2C6H)

• 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: (1,3,5-(CH3)3-2,6-(iPr2PCH2)2C6H)
• 英文别名: 2,4-bis[(diisopropylphosphino)methyl]mesitylene；1,3-bis(diisopropylphosphinomethylene)mesitylene；1,3,5-Me3-2,6-(CH2P(CHMe2)2)2-C6H；[3-[Di(propan-2-yl)phosphanylmethyl]-2,4,6-trimethylphenyl]methyl-di(propan-2-yl)phosphane
• 化学式: C₂₃H₄₂P₂
• 分子量: 380.534
• InChiKey: IKFYLXWUDJHPGO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  25
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (1,3,5-(CH3)3-2,6-(iPr2PCH2)2C6H) 在 chloro(1,5-cyclooctadiene)rhodium(I) dimer 氢气 作用下， 以 二氧六环-d8 为溶剂， 180.0 ℃ 、172.37 kPa 条件下， 反应 24.0h， 以32%的产率得到1,3-bis(diisopropylphosphinomethylene)xylene
  参考文献：
  名称：

  Catalytic selective cleavage of a strong C–C single bond by rhodium in solution

  摘要：

  [RhCl(C8H14)2]2与过量的二膦配体1,3-双(二异丙基磷氨基)美克斯烯1在双氧六烷中，在温和的氢气压力（25 psi）下反应，或与过量的HSi(OEt)3反应，导致强C-C单键的催化选择性断裂。

  DOI：

  10.1039/a800537k

文献信息

• Carbon−Carbon vs Carbon−Hydrogen Bond Activation by Ruthenium(II) and Platinum(II) in Solution
  作者：Milko E. van der Boom、Heinz-Bernhard Kraatz、Lawrence Hassner、Yehoshoa Ben-David、David Milstein

  DOI：10.1021/om990282f

  日期：1999.9.1

  the bisphosphine 1,3,5-(CH3)3-2,6-(iPr2PCH2)2C6H} (1) under 30 psi H2 results in quantitative C−C activation of an Ar−CH3 bond to afford Ru(Cl)(PPh3)2,6-(iPr2PCH2)2-3,5-(CH3)2C6H} (2) and CH4, whereas reaction of RuCl2(PPh3)3 with 1 in the presence of NaOtBu results in selective ArCH2−H bond activation to afford the benzylic complex Ru(Cl)(PPh3)1-CH2-2,6-(iPr2PCH2)2-3,5-(CH3)2C6H} (7). The identity

  的RuCl的反应2（PPH 3）3与双膦1,3,5-（CH 3）3 -2,6-（我镨2 PCH 2）2 C ^ 6 H}（1 30）根据PSIħ 2分的结果定量CC活化Ar-CH 3键得到Ru（Cl）（PPh 3）2,6-（i Pr 2 PCH 2）2 -3,5-（CH 3）2 C 6 H} （2）和CH 4，而RuCl的反应在NaO t Bu存在下具有1的2（PPh 3）3导致选择性的ArCH 2 -H键活化，从而提供苄基络合物Ru（Cl）（PPh 3）1-CH 2 -2,6-（i Pr 2 PCH 2）2 -3,5-（CH 3）2 C 6 H}（7）。通过双膦2,6-（i Pr 2 PCH 2）2 -3,5-（CH 3）的反应确认了16电子配合物2的身份。2 C 6 H 2 }（3），在膦臂之间缺少Ar-CH 3基，具有RuCl 2（PPh 3）3。也观察到金属插入到Ar-Et
• Synthesis and Structure of New Osmium−PCP Complexes. Osmium-Mediated C−C Bond Activation
  作者：Régis M. Gauvin、Haim Rozenberg、Linda J. W. Shimon、David Milstein

  DOI：10.1021/om000878z

  日期：2001.4.1

  The new complex Os1,3-((Pr2PCH2)-Pr-i)(2)C6H3}(Cl)(PPh3) (2) was obtained from the reaction between the diphosphine 1,3-((Pr2PCH2)-Pr-i)(2)C6H4} (1) and OsCl2(PPh3)(3). 2 reacts with H-2 to yield the dihydrido species Os1,3-((Pr2PCH2)-Pr-i)(2)C6H3}(H)(2)(Cl)(PPh3) (3). Addition of 1 equiv of carbon monoxide to 2 led to the formation of Os1,3-((Pr2PCH2)-Pr-i)(2)C6H3}(CO)(Cl)(PPH3) (4), while in the presence of excess CO, the bis-carbonyl complex Os1,3-((Pr2PCH2)-Pr-i)(2)C6H3}(CO)(2)-(Cl) (5) was formed. Both 2 and 5 were structurally characterized by X-ray diffraction studies. The reaction of OsCl2(PPh3)(3) (under hydrogen pressure) and OsHCl(PPh3)(3) with the diphosphine 1,3,5-(CH3)(3)-2,6-((Pr2PCH2)-Pr-i)(2)C6H} (6) led to the formation of the C-C activation products Os3,5-(CH3)-2,6-((Pr2PCH2)-Pr-i)(2)C6H}(H-2)(Cl) (7) and Os3,5-(CH3)-2,6-(Pr-i(2)-PCH2)(2)C6H}(Cl)(PPh3) (8), respectively.
• Nickel promoted C–H, C–C and C–O bond activation in solution
  作者：Milko E. van der Boom、Shyh-Yeon Liou、Linda J.W. Shimon、Yehoshoa Ben-David、David Milstein

  DOI：10.1016/j.ica.2004.06.002

  日期：2004.11

  Reaction of Nil(2) with the PCP-ligand 1-Et-2,6-((CH2PPr2)-Pr-/)(2)-C6H3} (1) results in selective activation of the strong sp(2)-sp(3) arylethyl bond to afford the aryl-nickel complex [Ni2,6-((CH2PPr2)-Pr-i)(2)-C6H3}I] (2), whereas reaction of Nil(2) with 1,3,5-(CH3)(3)-2,6((CH2PPr2)-Pr-i)(2)-C6H} (4) leads to the formation of the benzylic complex [Ni1-CH2-2,6-((CH2PPr2)-Pr-i)(2)-3,5-(CH3)(2)-C6H}I] (5) by selective C-H bond activation. Thermolysis of 5 results in formation of [Ni2,6-((CH2PPr2)-Pr-i)(2)-3,5-(CH3)(2)-C6H}I] (6) by activation of the sp(2)-sp(3) C-C bond. The identity of the new 16-electron complexes 2 and 6 was confirmed by reaction of NiI2 with 1,3-((CH2PPr2)-Pr-i)(2)-C6H4 (3) and 11,3-(CH3)(2)-4,6-((CH2PPr2)-Pr-i)(2)-C6H2) (7), respectively, lacking the aryl-alkyl groups between the "phosphines arms" (alkyl = ethyl, methyl). Complexes 2 and 5 have been fully characterized by X-ray analysis. Nickel-based activation of an unstrained C-O single bond was observed as well. Reaction of the aryl-methoxy bisphosphine 1-OMe-2,6(CH2-(PPr2)-Pr-i)-C6H3 (8) with NiI2 results in the formation of the phenoxy complex [Ni1-O-2,6-((CH2PPr2)-Pr-i)(2)-C6H3}I] (9) by selective sp(3)sp(3) C-O bond activation. (C) 2004 Elsevier B.V. All rights reserved.
• Activation of a non-strained C–C bond with plantinum(<scp>II</scp>)
  作者：Milko E. van der Boom、Heinz-Bernhard Kraatz、Yehoshoa Ben-David、David Milstein

  DOI：10.1039/cc9960002167

  日期：——

  The aromatic phosphine 1 reacts with (cod)PtCl2 to yield the C-H activation product 2; treatment of 2 with HCl results in overall selective functionalization of the strong Ar-Me bond to generate MeCl and the Ar-Pt complex 3.
• A Room Temperature Direct Metal Insertion into a Nonstrained Carbon−Carbon Bond in Solution. C−C vs C−H Bond Activation
  作者：Boris Rybtchinski、Arkadi Vigalok、Yehoshoa Ben-David、David Milstein

  DOI：10.1021/ja962253r

  日期：1996.1.1

  The diphosphine 1,3-bis[(di-tert-butylphosphino)methyl]-2,4,6-trimethylbenzene (la) upon reacting with the rhodium and iridium olefin complexes M(2)(olefin)(4)Cl-2 (M = Rh, Ir) undergoes rapid, selective metal insertion into the strong unstrained aryl-methyl bond under very mild conditions (room temperature), yielding CIM(CH3)-[C6H(CH3)(2)(CH2P(t-Bu)(2))(2)] (M = Rh (4a), Ir (7a)). The carbon-carbon bond activation is competitive with a parallel C-H activation process, which results in formation of complexes ClMH(L)[CH2C6H(CH3)(2)(CH2P(t-Bu)(2))(2)] (M = Rh (3a), Ir (6a); L = cyclooctene inthe case of 6a and is absent in 3a). Complexes 3a and 6a undergo facile C-H reductive elimination (at room temperature (3a) or upon moderate heating (6a)), followed by C-C oxidative addition, resulting in clean formation of 4a and 7a, respectively. The C-C bond activation products are stable under the reaction conditions, demonstrating that this process is the thermodynamically favorable one. X-ray single-crystal analysis of 4a demonstrates that the rhodium atom is located in the center of a square pyramid, with the methyl group occupying the position trans to the vacant coordination site. Direct kinetic comparison of the C-C and C-H activation processes shows that-in contrast to theoretical calculations-metal insertion into the carbon-carbon bond in this system is not only thermodynamically but also kinetically preferred over the competing insertion into the carbon-hydrogen bond. When the Ligand 1,3-bis[(di-tert-butylphosphino)methyl]-2,4, (Ib), bearing the strong electron-donating methoxy group in the position trans to the Ar-CH3 bond to be cleaved, was used instead of la, no effect on the reaction rate or on the ratio between the C-H and C-C activation products was observed. Our observations indicate that the C-C oxidative addition proceeds via a three-centered mechanism involving a nonpolar transition state, similar to the one proposed for C-H activation of hydrocarbons. An eta(2)-arene complex is not involved in the C-C activation process.