[Rh(η3-benzyl)(bis(diisopropylphosphino)ethane)]

• 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: [Rh(η3-benzyl)(bis(diisopropylphosphino)ethane)]
• 英文别名: (dippe)Rh(η3-CH2Ph)；(1,2-bis(diisopropylphosphanyl)ethane)η3-benzylrhodium；[Rh(η3-benzyl)(dippe)]
• 化学式: C₂₁H₃₉P₂Rh
• 分子量: 456.394
• InChiKey: JHDJEXWUIWPSMZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.31
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  [Rh(η3-benzyl)(bis(diisopropylphosphino)ethane)] 以 二氯甲烷 、 正戊烷 为溶剂， 生成 chloro[5,7-di(tert-butyl)-2,3-dihydro-3,3-dimethyl-1H-phosphindole-κP]((ethane-1,2-diyl)bis[diisopropylphosphine-κP])rhodium
  参考文献：
  名称：

  Generation and Reactivity of {(Ethane-1,2-diyl)bis[diisopropylphosphine-κP]}-{[2,4,6-tri(tert-butyl)phenyl]phosphino-κP}rhodium ([Rh{PH(tBu3C6H2)}(iPr2PCH2CH2PiPr2)]): Catalytic C−P Bond Formationvia Intramolecular C−H/P−H Dehydrogenative Cross-Coupling

  摘要：

  The complex [Rh(eta (3)-benzyl)(dippe)] (1: dippe = bis(diisopropylphosphino)ethane = (ethane-1,2-diyl)bis-[diisopropylphosphine]) reacted cleanly with Mes*PH2 (2; Mes* = 2,4,6-'Bu3C6H2) to provide a new Rh species [Rh(H)(dippe)(L)] (3). L being the 2,3-dihydro-3-3-dimethyl-1H-phosphindole ligind4(= 'Bu2C6H2(CMe2CH2PH)) (Scheme 1). Complex 3 was converted to the corresponding chloride [Rh(Cl)(dippe)(L)] (6) when treated with CH2Cl2, whereas the dimeric species [Rh-2{mu-'Bu2C6H2(CMe2CH2P)}(mu -H)(dippe)(2)] (7) was formed upon thermolysis in toluene (Scheme 2). The structures of 6 and 7(.)C(7)H(8) were determined by X-ray crystallography. Complexes 1 and 3 served as catalyst precursors for the dehydrogenative coupling of C-H and P-H bonds in the conversion of 2 to 4 (Scheme 3). Deuteration studies with Mes* PD2 exposed a complex series of bond-activation pathways that appear to involve C-H activation of the dippe ligand by the Rh-atom (Schemes 4 and 5).

  DOI：

  10.1002/1522-2675(20011017)84:10<2958::aid-hlca2958>3.0.co;2-l
• 作为产物：
  描述：

  (1,5-cyclooctadiene)Rh(η3-CH2Ph) 、 1,2-双(二-异丙基膦基)乙烷 以 正己烷 为溶剂， 以88%的产率得到[Rh(η3-benzyl)(bis(diisopropylphosphino)ethane)]
  参考文献：
  名称：

  的合成，结构和η氢化3 -苄基二膦铑和铱的络合物

  摘要：

  （COD）Rh组成的制备（η 3 -CH 2 PH）中描述从[（COD）的Rh]开始2（μ-Cl）的2通过加入任一的Zn（CH的2 PH）2或Mg（CH 2博士）2（THF）2。庞大的螯合二膦t Bu 2 P（CH 2）3 P t Bu 2，i Pr 2 P（CH 2）3 P i Pr 2，i Pr 2 P（CH 2）的添加）2 -P我镨2，我镨2 PCH 2 P我镨2和Cy 2 PCH 2 PCY 2至（COD）的Rh（η 3 -CH 2 PH）产生了配位不饱和，四配位的形式的铑络合物P 2的Rh（η 3 -CH 2 PH）。铱络合物的形式的对2的Ir（η 3 -CH 2 PH）（其中P 2 吨卜2 P（CH 2）3P t Bu 2和i Pr 2 P（CH 2）3 P i Pr 2）可以由[P 2 Ir] 2（μ-Cl）2和Zn（CH 2 Ph）2或Mg（CH 2 Ph）制备2（THF）2。苄基配合物与H

  DOI：

  10.1016/0022-328x(93)80212-t
• 作为试剂：
  描述：

  苯硫酚 、 二苯基膦 在 [Rh(η3-benzyl)(bis(diisopropylphosphino)ethane)] 作用下， 以 氘代苯 为溶剂， 反应 20.0h， 以77%的产率得到苯基硫代二苯基膦
  参考文献：
  名称：

  Selective Homo- and Heterodehydrocouplings of Phosphines Catalyzed by Rhodium Phosphido Complexes

  摘要：

  Reactions of the rhodium complex (dippe)Rh(eta3-CH2Ph) (1, dippe = iPr2PCH2CH2PiPr2) with ArPH2 (Ar = Ph, Mes) proceed via P-H oxidative additions to the phosphido complexes (dippe)Rh(mu-PHAr)2Rh(dippe) (3a, Ar = Ph; 3b, Ar = Mes). The corresponding reaction of Ph2PH occurs similarly, via the intermediate (dippe)Rh(PPh2)PHPh2 (4), to (dippe)Rh(mu-PPh2)2Rh(dippe) (3c). Complexes 3a-c and 4 are catalysts for the catalytic dehydrodimerizations of the corresponding phosphines to diphosphanes. Complex 1 is a more active dehydrocoupling catalyst, and substituent effects suggest that the active catalyst is mononuclear. Efficient dehydrocouplings of 2-EtC6H4PH2, 2-iPrC6H4PH2, and 2,4,6-iPr3C6H2PH2 were also observed. Complex 1 also catalyzes the heterocoupling of Ph2PH with PhSH (to Ph2P-SPh), and stoichiometric reactions in this system allowed isolation of (dippe)Rh(mu-SPh)2Rh(dippe) (6) and (dippe)Rh(SPh)PHR2 (7a, R2PH = MesPH2; 7b, R2PH = Ph2PH).

  DOI：

  10.1021/ja065346+

文献信息

• Fryzuk, Michael D.; McConville, David H.; Rettig, Steven J., Organometallics, 1993, vol. 12, # 6, p. 2152 - 2161
  作者：Fryzuk, Michael D.、McConville, David H.、Rettig, Steven J.

  DOI：——

  日期：——