Rh(H)(Cl)[tBuPCH2(C6H3)CH2PtBu2] | 60399-58-8

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: Rh(H)(Cl)[tBuPCH2(C6H3)CH2PtBu2]
• 英文别名: (2,6-bis{(di-tert-butylphosphino)methyl}phenyl)(chloro)(hydrido)rhodium(III)；Rh(Cl)(H)(2,6-(CH2P(t)Bu2)2C6H3)；Rh(H)(Cl)[^tBuPCH₂(C₆H₃)CH₂P^tBu₂]
• CAS: 60399-58-8
• 化学式: C₂₄H₄₄ClP₂Rh
• 分子量: 532.919
• InChiKey: DRWSVIQKBHVQDS-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  8.44
• 重原子数：
  28.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  Rh(H)(Cl)[tBuPCH2(C6H3)CH2PtBu2] 在 sodium hydroxide 作用下， 以 四氢呋喃 、 水 为溶剂， 以97%的产率得到(2,6-bis{(di-tert-butylphosphino)methyl}phenyl)(hydroxy)(hydrido)rhodium(III)
  参考文献：
  名称：

  {2,6-双[（二叔丁基膦基）甲基]苯基}二氢铑（III）还原二氧化碳

  摘要：

  DOI：

  10.1021/om00091a003
• 作为产物：
  描述：

  Rh(Cl)(CH2CH3)(2,6-(CH2P(t)Bu2)2C6H3) 以 二氧六环-d8 为溶剂， 生成 Rh(H)(Cl)[tBuPCH2(C6H3)CH2PtBu2]
  参考文献：
  名称：

  直接观察到的基于不饱和PCP的铑（III）-烷基络合物的β- H消除

  摘要：

  不饱和PCP型配合物Rh（L）{2,6-（CH 2 P t Bu 2）2 C 6 H 3 } X（L = Et，n Pr; X = Cl，I）配合物加热后转化为相应的Rh（III）配合物-hydride的Rh（H）{2,6-（CH 2 P吨卜2）2 C ^ 6 ħ 3 } X（X =氯，I）和乙烯或丙烯，产品指示的β - H消除过程。在我镨类似物时的Rh的反应中观察到（η 1 -N 2）{2,6-（CH 2 P吨在-10°C下具有i PrI的Bu 2）2 C 6 H 3 }，并在室温下容易分解，得到Rh（H）{2,6-（CH 2 P t Bu 2）2 C 6 H 3 } I和丙烯。缺乏β-氢的类似烷基络合物在所应用的反应条件下是稳定的。这种过程的机制进行了研究通过NMR，使用13 C和烷基配体的氘标记（L = ET- d 5，13 CH 2 CH 3）。13 C标记显示β- H的消除是不可逆的。观察到氘同位素效应k

  DOI：

  10.1021/om990073v
• 作为试剂：
  描述：

  一氧化碳 、 碘甲烷 在 Rh(H)(Cl)[tBuPCH2(C6H3)CH2PtBu2] 作用下， 190.0 ℃ 、2.8 MPa 条件下， 反应 3.0h， 生成 丙酸甲酯 、 溶剂黄146 、 丙酸
  参考文献：
  名称：

  WO2008/145976

  摘要：

  公开号：

文献信息

• Carbon−Carbon Bond Activation by Rhodium(I) in Solution. Comparison of sp²−sp³ vs sp³−sp³ C−C, C−H vs C−C, and Ar−CH₃ vs Ar−CH₂CH₃ Activation
  作者：Milko E. van der Boom、Shyh-Yeon Liou、Yehoshoa Ben-David、Michael Gozin、David Milstein

  DOI：10.1021/ja982345b

  日期：1998.12.1

  by reaction of the new Rh(η1-N2)2,6-(CH2PtBu2)2C6H3} (7) with EtI. It is possible to direct the bond activation process toward the benzylic C−H bonds of the aryl−alkyl group by choice of the Rh(I) precursor, of the substituents on the phosphorus atoms (tBu vs Ph), and of the alkyl moiety (Me vs Et). A Rh(III) complex which is analogous to the product of insertion into the ArCH2−CH3 bond (had it taken

  [RhClL2]2（L = 环辛烯或乙烯）与 2 当量的膦 1-Et-2,6-(CH2PtBu2)2C6H3} (1) 在甲苯中的反应导致选择性金属插入强 Ar-Et键。该反应在没有激活较弱的 sp3-sp3 ArCH2-CH3 键的情况下进行。通过新的 Rh(η1-N2)2,6-(CH2PtBu2)2,6-(CH2PtBu2) 反应制备碘化物类似物 6，证实了配合物 Rh(Et)2,6-(CH2PtBu2)2C6H3}Cl (3) 的身份2C6H3} (7) 与 EtI。通过选择 Rh(I) 前体、磷原子上的取代基（tBu vs Ph）和烷基部分，可以将键活化过程导向芳基-烷基的苄基 C-H 键（我对 Et）。制备了类似于插入到 ArCH2- 键中的产物的 Rh(III) 络合物（如果它发生了），并且表明它不是 Ar-CH2 键活化过程中的中间体。因此，在该系统中，Rh(I)
• Kinetics and Thermodynamics of Small Molecule Binding to Pincer-PCP Rhodium(I) Complexes
  作者：Mark D. Doherty、David C. Grills、Kuo-Wei Huang、James T. Muckerman、Dmitry E. Polyansky、Rudi van Eldik、Etsuko Fujita

  DOI：10.1021/ic300672g

  日期：2013.4.15

  The kinetics and thermodynamics of the binding of several small molecules, L (L = N2, H2, D2, and C2H4), to the coordinatively unsaturated pincer-PCP rhodium(I) complexes Rh[tBu2PCH2(C6H3)CH2PtBu2] (1) and Rh[tBu2P(CH2)2(CH)(CH2)2PtBu2] (2) in organic solvents (n-heptane, toluene, THF, and cyclohexane-d12) have been investigated by a combination of kinetic flash photolysis methods, NMR equilibrium

  几个小分子L（L = N 2，H 2，D 2和C 2 H 4）与配位不饱和钳式PCP铑（I）配合物Rh [ t Bu 2 PCH 2（C 6 H 3）CH 2 P t Bu 2 ]（1）和Rh [ t Bu 2 P（CH 2）2（CH）（CH 2）2 P t Bu 2 ]（2结合动力学快速光解法，NMR平衡研究和密度泛函理论（DFT）计算，研究了有机溶剂（正庚烷，甲苯，THF和环己烷d 12）中的）。使用各种气体混合物并通过NMR监测直至建立平衡，发现环己烷-d 12中N 2，H 2和C 2 H 4的结合相对自由能按C 2 H 4
• A highly active alkane dehydrogenation catalyst: stabilization of dihydrido rhodium and iridium complexes by a P–C–P pincer ligand
  作者：Mukta Gupta、Chrystel Hagen、Robert J. Flesher、William C. Kaska、Craig M. Jensen

  DOI：10.1039/cc9960002083

  日期：——

  The novel P-C-P pincer complex, [IrH2C6H3(CH(2)PBu(2)(t))(2)-2,6}] has long-term stability at 200 degrees C and catalyses the transfer dehydrogenation of cyclooctane to cyclooctene at the rate of 12 turnovers min(-1).
• Alkyl− and Aryl−Oxygen Bond Activation in Solution by Rhodium(I), Palladium(II), and Nickel(II). Transition-Metal-Based Selectivity
  作者：Milko E. van der Boom、Shyh-Yeon Liou、Yehoshoa Ben-David、Linda J. W. Shimon、David Milstein

  DOI：10.1021/ja9738889

  日期：1998.7.1

  Reaction of [RhCl(C8H14)(2)](2) (C8H14 = cyclooctene)with 2 equiv of the aryl methyl ether phosphine 1 in C6D6 results in an unprecedented metal insertion into the strong sp(2)-sp(3) aryl-O bond. This remarkable reaction proceeds even at room temperature and occurs directly, with no intermediacy of C-H activation or insertion into the adjacent weaker ArO-CH3 bond. Two new phenoxy complexes (8 and 9), which are analogous to the product of insertion into the ArO-CH3 bond (had it taken place) were prepared and shown not to be intermediates in the Ar-OCH3 bond cleavage process. Thus, aryl-O bond activation by the nucleophilic Rh(I) is kinetically preferred over activation of the alkyl-O bond. The phenoxy Rh(I)-eta(1)-N-2 complex (8) is in equilibrium with the crystallographically characterized Rh(I)-mu-N-2-Rh(I) dimer (12). Reaction of [RhCl(C8H14)(2)](2) With 2 equiv of the aryl methyl ether phosphine 2, PPh3, and excess HSiR3 (R = OCH2CH3, CH2CH3) results also in selective metal insertion into the aryl-O bond and formation of (CH3O)SiR3. Thus, transfer of a OCH3 group from carbon to silicon was accomplished, showing that hydrosilation of an unstrained aryl-O single bond by a primary silane is possible. The selectivity of C-O bond activation is markedly dependent on the transition-metal complex and the alkyl group involved, allowing direction of the C-O bond activation process at either the aryl-O or alkyl-O bond. Thus, contrary to the reactivity of the rhodium complex, reaction of NiI2 or Pd(CF3CO2)(2) with 1 equiv of 1 in ethanol or C6D6 at elevated temperatures results in exclusive activation of the sp(3)-sp(3) ArO-CH3 bond, while reaction of the analogous aryl ethyl ether 4 and Pd(CF3CO2)(2) results in both sp(3)-sp(3) and sp(2)-sp(3) C-O bond activation. The resulting phenoxy Pd(II) complex (18) is fully characterized by X-ray analysis. Heating the latter under mild dihydrogen pressure results in hydrodeoxygenation to afford an aryl-Pd(II) complex (19).
• Interaction of {2,6-bis[(di-tert-butylphosphino)methyl]phenyl}rhodium(I) with hydrocarbons. X-ray molecular structure of {2,6-bis[(di-tert-butylphosphino)methyl]phenyl}chlorohydridorhodium(III)
  作者：S. Nemeh、C. Jensen、E. Binamira-Soriaga、W. C. Kaska

  DOI：10.1021/om50004a034

  日期：1983.10