[Rh(dippe)(μ-SC6H5)]2 | 701255-92-7

• 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(dippe)(μ-SC6H5)]2
• 英文别名: bis(1,2-bis(diisopropylphosphanyl)ethane)bis(μ-SPh)dirhodium
• CAS: 701255-92-7
• 化学式: C₄₀H₇₄P₄Rh₂S₂
• 分子量: 948.866
• InChiKey: SMNNSNNLOFXSFE-UHFFFAOYSA-L

反应信息

• 作为产物：
  描述：

  [(1,2-bis(diisopropylphosphino)ethane)Rh]2(μ-H)2 、 苯硫酚 以 正己烷 为溶剂， 以85%的产率得到[Rh(dippe)(μ-SC6H5)]2
  参考文献：
  名称：

  Structural properties and inversion mechanisms of [Rh(dippe)(μ-SR)]2 complexes

  摘要：

  Several new bis-thiolate complexes of the type [Rh(dippe)(mu-SR)](2) where R = H, methyl, cyclohexyl, o-biphenyl, and phenyl, or (SR)(2)=SCH2CH2CH2S have been synthesized and characterized by NMR spectroscopy and single crystal X-ray diffraction. All [Rh(dippe)(mu-SR)](2) Complexes except [Rh(dippe)(mu-SPh)](2) exhibit bent geometries, while the orientation of the thiolato substituents changes with increasing steric bulk. H-1 and P-31 NMR spectroscopies indicate that both ring inversion and sulfur inversion occur among the members of the series, which allows them to access several isomeric forms when they are in solution. I I P NMR spectroscopy indicates that sulfur inversion in [Rh(dippe)(mu-SH)](2), [Rh(dippe)(mu-Sbiphenyl)](2), and [Rh(dippe)(mu-SPh)](2) is a non-dissociative process. (C) 2003 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2003.11.026

文献信息

• Selective Homo- and Heterodehydrocouplings of Phosphines Catalyzed by Rhodium Phosphido Complexes
  作者：Li-Biao Han、T. Don Tilley

  DOI：10.1021/ja065346+

  日期：2006.10.1

  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).