cis-Pt(PEt3)2(H)(SiPh3) | 201860-25-5

• 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: cis-Pt(PEt3)2(H)(SiPh3)
• 英文别名: cis-[Pt(H)(SiPh3)(PEt3)2]
• CAS: 201860-25-5
• 化学式: C₃₀H₄₆P₂PtSi
• 分子量: 691.808
• InChiKey: QMVRSBCDGUVVGH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.99
• 重原子数：
  34.0
• 可旋转键数：
  12.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  chlorotris(triethylphosphane-κ-P)rhodium(I) 、 cis-Pt(PEt3)2(H)(SiPh3) 生成 trans-chlorohydridobis(triethylphosphine)platinum(II)
  参考文献：
  名称：

  Intermolecular Transfer of Triarylsilane from RhCl(H)(SiAr₃)[P(i-Pr)₃]₂ to a Platinum(0) Complex, Giving cis-PtH(SiAr₃)(PEt₃)₂ (Ar = C₆H₅, C₆H₄F-p, C₆H₄Cl-p)

  摘要：

  Chlorohydrido(triarylsilyl)rhodium(III) complexes RhCl(H)(SiAr3)[P(i-Pr)(3)](2) (1a, Ar = C6H5; 1b, Ar = C6H4F-p; 1c, Ar = C6H4Cl-p) react with Pt(PEt3)(4) to give mixtures of cis-PtH(SiAr3)(PEt3)(2) (2a, Ar = C6H5; 2b, Ar = C6H4F-p; 2c, C6H4Cl-p) and RhCl(PEt3)(3). Complexes 2a-c have been characterized by X-ray crystallography and/or NMR spectroscopy.

  DOI：

  10.1021/om9706976
• 作为产物：
  描述：

  Rh(H)(Cl)(P(iPr)3)2(Si(C6H5)3) 以 氘代苯 、 正戊烷 为溶剂， 生成 cis-Pt(PEt3)2(H)(SiPh3)
  参考文献：
  名称：

  Intermolecular Transfer of Triarylsilane from RhCl(H)(SiAr₃)[P(i-Pr)₃]₂ to a Platinum(0) Complex, Giving cis-PtH(SiAr₃)(PEt₃)₂ (Ar = C₆H₅, C₆H₄F-p, C₆H₄Cl-p)

  摘要：

  Chlorohydrido(triarylsilyl)rhodium(III) complexes RhCl(H)(SiAr3)[P(i-Pr)(3)](2) (1a, Ar = C6H5; 1b, Ar = C6H4F-p; 1c, Ar = C6H4Cl-p) react with Pt(PEt3)(4) to give mixtures of cis-PtH(SiAr3)(PEt3)(2) (2a, Ar = C6H5; 2b, Ar = C6H4F-p; 2c, C6H4Cl-p) and RhCl(PEt3)(3). Complexes 2a-c have been characterized by X-ray crystallography and/or NMR spectroscopy.

  DOI：

  10.1021/om9706976

文献信息

• Activation of Si–Si and Si–H bonds at Pt: a catalytic hydrogenolysis of silicon–silicon bonds
  作者：Jan Voigt、Maren A. Chilleck、Thomas Braun

  DOI：10.1039/c3dt32530j

  日期：——

  The activation of Ph2HSiSiHPh2 and Me3SiSiMe3 at [Pt(PEt3)3] (1) yielded the products of oxidative addition. The formation of [Pt(SiHPh2)2(PEt3)2] (2) as a mixture of the cis and trans isomers appears to proceed quantitatively, whereas a conversion to give cis-[Pt(SiMe3)2(PEt3)2] (3) was not complete. Treatment of 1 with one equivalent of H2SiPh2 led to cis-and trans-[Pt(H)(SiHPh2)(PEt3)2] (cis-4, trans-4) together with the dinuclear complex [(Et3P)2(H)Pt(μ-SiPh2)(μ–η2-HSiPh2)Pt(PEt3)] (5). In contrast, HSiMe3 reacts with [Pt(PEt3)3] to yield cis-[Pt(H)(SiMe3)(PEt3)2] (7) exclusively. Catalytic reactions of dihydrogen with the disilanes Ph2HSiSiHPh2 or Me3SiSiMe3 in the presence of catalytic amounts of [Pt(PEt3)3] (1) led to the products of hydrogenolysis, H2SiPh2 and HSiMe3. The conversion of Me3SiSiMe3 is much slower and needs higher temperature to proceed.

  由 [Pt(PEt3)3] (1) 引发的 Ph2HSiSiHPh2 和 Me3SiSiMe3 的氧化加成反应，得到了相应的产物。[Pt(SiHPh2)2(PEt3)2] (2) 的形成以顺反异构体的混合物形式进行，且似乎是定量反应，而生成顺式-[Pt(SiMe3)2(PEt3)2] (3) 的转化并没有完全进行。用等当量的 H2SiPh2 处理 1 得到了顺式和反式-[Pt(H)(SiHPh2)(PEt3)2] (顺式-4，反式-4) 以及双核配合物 [(Et3P)2(H)Pt(μ-SiPh2)(μ-η2-HSiPh2)Pt(PEt3)] (5)。相比之下，HSiMe3 与 [Pt(PEt3)3] 反应仅生成顺式-[Pt(H)(SiMe3)(PEt3)2] (7)。在催化量的 [Pt(PEt3)3] (1) 存在下，二氢与二硅烷 Ph2HSiSiHPh2 或 Me3SiSiMe3 的催化反应生成了氢解产物 H2SiPh2 和 HSiMe3。Me3SiSiMe3 的转化速度更慢，需要更高的温度才能进行。
• Si–H and Si–Si activation at Pt: synthesis and reactivity of neutral and cationic silyl complexes
  作者：Jan Voigt、Thomas Braun

  DOI：10.1039/c1dt11351h

  日期：——

  Reactions of [Pt(PEt3)3] (1) with the silanes HSiPh3, HSiPh2Me and HSi(OEt)3 led to the products of oxidative addition, cis-[Pt(H)(SiPh3)(PEt3)2] (2), cis-[Pt(H)(SiPh2Me)(PEt3)2] (3), cis-[Pt(H)Si(OEt)3}(PEt3)2] (cis-4) and trans-[Pt(H)Si(OEt)3}(PEt3)2] (trans-4). The complexes cis-4 and trans-4 can also be generated by hydrogenolysis of (EtO)3SiSi(OEt)3 in the presence of 1. Furthermore, the silyl compounds cis-4 and trans-4 react with B(C6F5)3 and CH3CN by hydride abstraction to give the cationic silyl complex trans-[PtSi(OEt)3}(NCCH3)(PEt3)2][HB(C6F5)3] (8). In addition, the reactivity of the complexes cis-4, trans-4 and 8 towards alkenes and CO was studied using NMR experiments.

  Pt(PEt3)3] (1) 与硅烷 HSiPh3、HSiPh2Me 和 HSi(OEt)3 反应生成氧化加成产物、顺式-[Pt(H)(SiPh3)(PEt3)2] (2)、顺式-[Pt(H)(SiPh2Me)(PEt3)2] (3)、顺式-[Pt(H)Si(OEt)3}(PEt3)2] (cis-4) 和反式-[Pt(H)Si(OEt)3}(PEt3)2] (trans-4) 复合物。顺式-4 和反式-4 复合物也可以在 1 的存在下通过氢解 (EtO)3SiSi(OEt)3 生成。此外，顺式-4 和反式-4 硅烷基化合物通过氢化物萃取与 B(C6F5)3 和 CH3CN 反应生成阳离子硅烷基复合物反式-[PtSi(OEt)3}(NCCH3)(PEt3)2][HB( )3] (8)。此外，还利用核磁共振实验研究了顺式-4、反式-4 和 8 复合物对烯和 CO 的反应性。