| 848093-89-0

• CAS: 848093-89-0
• 化学式: C₁₈H₂₉PRu
• 分子量: 377.472
• InChiKey: MPKASSXTGSLTHG-UHFFFAOYSA-N

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：

  、 三氯硅烷 以 正己烷 、 甲苯 为溶剂， 以63%的产率得到
  参考文献：
  名称：

  Syntheses and X-ray Diffraction Studies of Half-Sandwich Hydridosilyl Complexes of Ruthenium

  摘要：

  The reactions of a series of half-sandwich trihydrides of ruthenium, Cp*(R3P)Ru(H)(3) (R3P = (Pr3P)-P-i, (Pr2MeP)-Me-i, (PrMe2P)-Me-i, PhMe2P), with a family of chlorosilanes (ClSiHMe2, Cl2SiHMe, Cl3SiH) have been studed with the aim of preparing the dihydridesilyl derivatives Cp*(R3P)Ru(H)(2)(SiR3). The reaction of Cp*(R3P)Ru(H)(3) with ClSiHMe2 occurs at 90 degreesC and gives two types of products, Cp*(R3P)Ru(H)(2)(SiClMe2) (1) and Cp*(R3P)Ru(H)(2)(SiCl2Me) (2). The yield of complexes 2 increases with the decrease of the size of the phosphine ligand. X-ray structures of Cp*((Pr3P)-P-i)Ru(H)(2)(SiClMe2) (1a) and Cp*((Pr2MeP)-Me-i)Ru(H)(2)(SiClMe2) (1b) are consistent with the presence of interligand hypervalent interactions Ru-H...Si-Cl. The compounds Cp*(R3P)Ru(H)(Cl)(SiCl2Me) (3) were prepared by the reaction of Cp*(R3P)Ru(H)(3) with Cl2SiHMe at 60 degreesC and characterized by NMR and IR spectroscopy. Complex Cp*(Pr-3(i) P)Ru(Cl)(SiCl2Me)(H) (3a) reacts with excess PMe3 to give the H-Si elimination product Cp*(PMe3)(2)RuCl. The reactions of Cp*(R3P)Ru(H)(3) (R3P = (Pr3P)-P-i, (Pr2MeP)-Me-i) with Cl2SiHMe in the presence of NEt3 at 90 degreesC give the dihydridesilyls Cp*(R3P)Ru(H)(2)(SiCl2Me) (R3P = (Pr3P)-P-i (2a), R3P = (Pr2MeP)-Me-i (2b)). X-ray structures of these products may be rationalized as containing a double interiligand hypervalent interaction Ru-H-2...Si-Cl-2. NMR reaction between Cp*((MePr2P)-P-i)Ru(H)(3) and excess Cl3SiMe at 100 degreesC resulted in a clean formation of Cp*((MePr2P)-P-i)Ru(H)(Cl)(SiCl2Me). Complexes Cp*(R3P)Ru(Cl)(SiCl3)(H) (5) were prepared by the reaction of Cp*(R3P)Ru(H)(3) with Cl3SiH at room temperature and characterized by NMR and IR spectroscopy. The reactions of Cp*(R3P)Ru(H)(3) (R3P = (Pr3P)-P-i, (Pr2MeP)-Me-i) with Cl3SiH in the presence of NEt3 at 60 degreesC give the dihydridesilyls Cp*(R3P)Ru(H)(2)(SiCl2H) (R3P = (Pr3P)-P-i (6a), R3P = (Pr2MeP)-Me-i (6b)) along with a mixture of some other compounds, whereas the analogous reactions in the presence of (NPr2Et)-Et-i afford the dihydridesilyls Cp*(R3P)Ru(H)(2)(SiClH2) (R3P = (Pr3P)-P-i (7a), R3P = (Pr2MeP)-Me-i (7b)). Complex Cp*((Pr3P)-P-i)RuH2(SiH3) (8a), prepared by the reduction of Cp*((Pr3P)-P-i)Ru(Cl)(SiCl3)(H) (5a) by LiAlH4, reacts with [NHMe2Ph]Cl to give a mixture of Cp*((Pr3P)-P-i)Ru(H)(3) and Cp*((Pr3P)-P-i)Ru(H)(2)(SiClH2) (7a).The crystal structures of 1a,1b, 2a, 2c, 5b, 5c, 5d, and 8a have been determined by X-ray structure analysis.

  DOI：

  10.1021/om0495271

文献信息

• Activation and Dehydrogenative Silylation of the C–H Bonds of Phosphine-coordinated Ruthenium in Lu/Ru Heteromultimetallic Hydride Complexes
  作者：Takanori Shima、Zhaomin Hou

  DOI：10.1246/cl.2008.298

  日期：2008.3.5

  The reaction of half-sandwich lutetium dialkyl complex Cp∗Lu(CH2SiMe3)2(THF) (Cp∗= C5Me5) with ruthenium–trihydrido–phosphine complexes Cp∗Ru(PR3)H3 (R3 = Ph3, Ph2Me, PhMe2, and Me3) at 50 °C afforded the corresponding Lu/Ru heterobimetallic dihydride complexes, which was accompanied by selective C–H bond activation of the phosphine ligand. The reaction of such a resulting phosphinomethyl-bridged Lu/Ru complex with PhSiH3 led to selective dehydrogenative silylation at the “CH2” unit.

  半夹心镥二烷基络合物 Cp*Lu( SiMe3)2(THF) (Cp*= C5Me5) 与钌三氢膦络合物 Cp*Ru(PR3)H3 (R3 = Ph3、Ph2Me、PhMe2 和 Me3) 的反应）在50℃下得到相应的Lu/Ru异双金属二氢化物配合物，伴随着膦配体的选择性C-H键活化。由此产生的膦甲基桥联的 Lu/Ru 络合物与 PhSiH3 的反应导致“CH2”单元选择性脱氢甲硅烷基化。