[(1,2-bis(diisopropylphosphino)ethane)Rh]2(μ-H)(μ-η(2)-SiH(C6H5)2) | 135525-09-6

• 英文名称: [(1,2-bis(diisopropylphosphino)ethane)Rh]2(μ-H)(μ-η(2)-SiH(C6H5)2)
• CAS: 135525-09-6；178106-54-2
• 化学式: C₄₀H₇₆P₄Rh₂Si
• 分子量: 914.835
• InChiKey: FWARFICUBGHCAQ-UHFFFAOYSA-N

计算性质

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

• 作为反应物：
  描述：

  [(1,2-bis(diisopropylphosphino)ethane)Rh]2(μ-H)(μ-η(2)-SiH(C6H5)2) 以 正己烷 、 氘代甲苯 为溶剂， 生成 [(1,2-bis(diisopropylphosphino)ethane)Rh]2(μ-H)(μ-η(2)-SiH(CH3)(C6H4CH3))
  参考文献：
  名称：

  Dimeric Rhodium μ-Silylene and μ-η²-Silyl Complexes:  Catalytic Silicon−Silicon Bond Formation and X-ray Structures of [{Prⁱ₂PCH₂CH₂PPrⁱ₂}Rh]₂(μ-SiRR‘)₂ (R = R‘ = Ph and R = Me, R‘ = Ph) and [{Prⁱ₂PCH₂CH₂PPrⁱ₂}Rh(H)]₂(μ-η²-H−SiMe₂)₂

  摘要：

  The stoichiometric and catalytic reactions of secondary silanes with the rhodium hydride bridged dimer [(dippe)Rh](2)(mu-H)(2) (1; dippe = 1,2-bis(diisopropylphosphino)ethane) are described. The reaction of 1 with Ph2SiH2 results in the formation of the bis(mu-silylene) complex [(dippe)Rh](2)(mu-SiPh2)(2) (2a); a similar reaction ensues upon addition of MePhSiH2 or Me(p)TolSiH(2) ((P)Tol =p-tolyl) to 1 except that the bis(silylene) complexes exist as a mixture of cis and trans stereoisomers. Dimethylsilane reacts with 1 to generate the dinuclear complex [(dippe)Rh(H)](2)(mu-eta(2)-SiMe2)(2) (4d). The hydride dimer acts as a catalyst precursor for the dimerization of excess Ph2SiH2 to tetraphenyldisilane (Ph2SiHSiHPh2). A catalytic cycle is proposed that consists of dinuclear intermediates.

  DOI：

  10.1021/om980651s
• 作为产物：
  描述：

  {(1,2-bis(diisopropylphosphino)ethane)Rh}2(μ-SiPh2)2 以 氘代甲苯 、 甲苯 为溶剂， 生成 [(1,2-bis(diisopropylphosphino)ethane)Rh]2(μ-H)(μ-η(2)-SiH(C6H5)2)
  参考文献：
  名称：

  Dimeric Rhodium μ-Silylene and μ-η²-Silyl Complexes:  Catalytic Silicon−Silicon Bond Formation and X-ray Structures of [{Prⁱ₂PCH₂CH₂PPrⁱ₂}Rh]₂(μ-SiRR‘)₂ (R = R‘ = Ph and R = Me, R‘ = Ph) and [{Prⁱ₂PCH₂CH₂PPrⁱ₂}Rh(H)]₂(μ-η²-H−SiMe₂)₂

  摘要：

  The stoichiometric and catalytic reactions of secondary silanes with the rhodium hydride bridged dimer [(dippe)Rh](2)(mu-H)(2) (1; dippe = 1,2-bis(diisopropylphosphino)ethane) are described. The reaction of 1 with Ph2SiH2 results in the formation of the bis(mu-silylene) complex [(dippe)Rh](2)(mu-SiPh2)(2) (2a); a similar reaction ensues upon addition of MePhSiH2 or Me(p)TolSiH(2) ((P)Tol =p-tolyl) to 1 except that the bis(silylene) complexes exist as a mixture of cis and trans stereoisomers. Dimethylsilane reacts with 1 to generate the dinuclear complex [(dippe)Rh(H)](2)(mu-eta(2)-SiMe2)(2) (4d). The hydride dimer acts as a catalyst precursor for the dimerization of excess Ph2SiH2 to tetraphenyldisilane (Ph2SiHSiHPh2). A catalytic cycle is proposed that consists of dinuclear intermediates.

  DOI：

  10.1021/om980651s

文献信息

• Reactions of Secondary Silanes with [{Prⁱ₂PCH₂CH₂PPrⁱ₂}Rh]₂(μ-H)₂. A Series of Dinuclear Silyl−Hydride Complexes and Their Possible Involvement in the Catalytic Hydrosilylation of Olefins
  作者：Michael D. Fryzuk、Lisa Rosenberg、Steven J. Rettig

  DOI：10.1021/om950450d

  日期：1996.6.25

  Addition of a 1 equiv of a secondary silane (RR'SiH2) to [(dippe)Rh](2)(mu-H)(2) (1) gives the complexes [(dippe)Rh](2)(mu-H)(mu-eta(2)-HSiRR') (2a, R = R' = Ph; 2b, R = R' = Me; 2c, R = Ph, R' = Me; dippe = 1,2-bis(diisopropylphosphino)ethane). X-ray diffraction studies of 2a,b confirm the presence of a three-center, two-electron, Rh-H-Si bond. The observed fluxionality of 2a-c in solution is due to exchange of the silicon and rhodium hydrides. Complexes 2a-c lose hydrogen in the presence of 1 equiv of carbon monoxide to give complexes 3a-c, [(dippe)Rh](2)(mu-SiRR')(mu-CO). A catalytic cycle is proposed for the hydrosilylation of olefins by diphenylsilane to give Ph(2)SiR(2) (R = Et) or Ph(2)SiHR (R = Bu), which occurs in the presence of 1, One of the active species is thought to be [(dippe)Rh](2)(mu-H)(mu-eta(2)-HSiPh(2)) (2a).