Cp*RhCl(Ph)(PMe3) | 88704-28-3

• 英文名称: Cp*RhCl(Ph)(PMe3)
• 英文别名: Cp*RhCl(Ph)(PMe₃)；[Cp(*)Rh(Ph)(PMe3)Cl]
• CAS: 88704-28-3
• 化学式: C₁₉H₂₉ClPRh
• 分子量: 426.772
• InChiKey: XLLVSOCMPXPJJJ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  Cp*RhCl(Ph)(PMe3) 在 Na(+){H₂Al(OCH₂CH₂OCH₃)2}(-) 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 以85%的产率得到[Rh(H)(Ph)(η5-pentamethylcyclopentadienyl)(PMe3)]
  参考文献：
  名称：

  (C5Me5)Rh(PMe3)(R)H中烷烃和芳烃碳氢键活化的机理和热力学

  摘要：

  使用整体激活参数生成 C/sub 6/H/sub 6/ 和 (C/sub 5/Me/sub 5/)Rh(PMe/sub 3/)(C/sub 6/D/sub 5/)D delta H/sup +/-30.5 +/- 0.8 kcal/mol 和 ..delta..S/sup +/-14.9+/- 2.5 eu。烷基和芳基氢化物复合物也可以通过在烷烃存在下从 (C/sub 5/Me/sub 5/)Rh(PMe/sub 3/)H/sub 2/ 光化学挤出 H/sub 2/ 产生或芳烃溶剂。在竞争实验中，苯对环戊烷的选择性为 5.4:1，在 -35/sup 0/C 时表现出。在-45/sup 0/C 的甲苯溶剂中辐照产生的产物中，观察到甲苯的所有可能 CH 键的活化增加了 57% » 间位、36% 对位、7% 邻位和 <1% 苄基。苯和甲苯、间二甲苯、邻二甲苯或对二甲苯的活化之间的热力学控制竞争显示出对苯的偏好为

  DOI：

  10.1021/ja00318a018
• 作为产物：
  描述：

  (η5-C5Me5)(PMe3)Rh(H)2 、 氘代苯 在 四氯化碳 、 苯 作用下， 以 四氯化碳 、 氘代苯 、 苯 为溶剂， 生成 Cp*RhCl(Ph)(PMe3) 、
  参考文献：
  名称：

  Isotope effects in arene carbon-hydrogen bond activation by [(C5Me5)Rh(PMe3)]

  摘要：

  DOI：

  10.1021/ja00276a019

文献信息

• Insertion of SO₂ into the Metal−Carbon Bonds of Rhodium and Iridium Compounds, and Reactivity of the SO₂-Inserted Species
  作者：Laurent Lefort、Rene J. Lachicotte、William D. Jones

  DOI：10.1021/om971030m

  日期：1998.3.1

  Sulfur dioxide has been found to insert into the metal−carbon bonds of both rhodium and iridium alkyl and aryl complexes. The sulfinate ligand can be removed with a strong acid such as HCl, generating free sulfinic acid. Acids with weakly coordinating anions protonate the sulfinate oxygen, but the sulfinic acid remains bound to the metal center. Added sulfinic acids can exchange with the coordinated

  已经发现二氧化硫插入到铑和铱烷基和芳基络合物的金属碳键中。可以用强酸（例如HCl）除去亚磺酸盐配体，生成游离亚磺酸。具有弱配位阴离子的酸会使亚磺酸氧质子化，但亚磺酸仍与金属中心键合。添加的亚磺酸可以与配位的亚磺酸酯基交换。
• 1,4-Metal migration in a Cp*Rh(iii) complex
  作者：Yousuke Ikeda、Koichi Takano、Shintaro Kodama、Youichi Ishii

  DOI：10.1039/c3cc46700g

  日期：——

  The reaction of [Cp*RhCl(Ph)(PR3)] (R = Ph or Me) with internal alkynes in the presence of NaBArF4 affords the o-vinylaryl complex with a Rh-(vinyl CH) agostic interaction by way of the alkyne insertion followed by 1,4-rhodium migration, providing the first example of the 1,4-migration of a Rh(III) center.

  [Cp*RhCl(Ph)(PR3)] (R = Ph或Me) 在NaBArF4存在下与内部炔烃反应，生成具有Rh-(乙烯CH)亲核相互作用的o-乙烯芳香族络合物，该反应通过炔烃插入后紧接着进行的1,4-铑迁移，提供了Rh(III)中心1,4-迁移的首个例子。
• Aromatic and aldehyde carbon–hydrogen bond activation at cationic Rh(III) centers. Evaluation of electronic substituent effects on aldehyde binding and C–H oxidative addition
  作者：Britton K. Corkey、Felicia L. Taw、Robert G. Bergman、Maurice Brookhart

  DOI：10.1016/j.poly.2004.09.005

  日期：2004.11

  Cationic rhodium methyl complexes, [Cp-*(PMe3)Rh(Me)(CH2Cl2)]BAr4' (1) and [Cp-*(P(OMe)(3))Rh(Me)(CH2Cl2)]BAr4' (3), react with benzene to yield the corresponding phenyl complexes, [Cp-*(PMe3)Rh(Ph)(CH2Cl2)]BAr4' (6) and [Cp-*(P(OMe)(3))Rh(Ph)(CH2Cl2)]BAr4' (7). First-order rate constants observed in 1.1 M benzene in CD2Cl2 at 25 degreesC are (2.1 +/- 0.2) x 10(-5) s(-1) and (1.9 +/- 0.2) x 10(-5) s(-1), respectively. Reactions of 1 and 3 with p-X-substituted benzaldehydes (X = -CF3, -CH3, and -OMe) initially produce the sigma-aldehyde adducts, [Cp-*(L)Rh(Me)(p-XC6H4CHO)]BAr4' (L = PMe3 (15), P(OMe)(3) (16)). Exchange of free with bound aldehyde occurs via a dissociative process and quantitative NMR rate measurements show that complexes of 1 exchange faster than those of 3 and that less basic aldehydes exchange faster than more basic aldehydes (p-CF3C6H4CHO > p-CH3C6H4CHO > p-CH3OC6H4CHO). The aldehyde adducts undergo C-H bond activation to produce initially methane plus acyl aldehyde adducts, [Cp-*(L)Rh(C(O)C6H4X)(p - XC6H4CHO)]BAr4' (L = PMe3 (17), P(OMe)(3) (18)). Rates of C-H activation are correlated with aldehyde exchange rates; activation barriers of weakly bound aldehydes are lower than more strongly bound aldehydes. In the case of L = PMe3, decarbonylation of the aldehyde adducts occurs cleanly to form aryl carbonyl complexes, [Cp-*(PMe3)Rh(C6H4X)(CO)]BAr4'. For L = P(OMe)(3), decarbonylation is a more complicated process; some intermediates and products have been identified by NMR spectroscopy. (C) 2004 Elsevier Ltd. All rights reserved.