[Cp(PMe3)2RuH2]Cl | 160158-78-1

• 英文名称: [Cp(PMe3)2RuH2]Cl
• CAS: 160158-78-1
• 化学式: C₁₁H₂₅P₂Ru*Cl
• 分子量: 355.79
• InChiKey: AXEGLECJWZGPLP-UHFFFAOYSA-M

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：

  [Cp(PMe3)2RuH2]Cl 以 氘代苯 为溶剂， 生成 chlorocyclopentadienylbis(trimethylphosphine)ruthenium(II)
  参考文献：
  名称：

  辅助基团对（含）Cp（PR 3）2 Ru的硅烷基钌配合物的制备及光谱性质的影响

  摘要：

  Cp（PR 3）2 RuSiX 3 [PR 3 = PPhMe 2，SiX 3 = SiCl 3（1），SiHCl 2（2），SiH 2 Cl（3），SiHMeCl（4），SiH 3（7），SiMeH 2（8），SiMe 3（9）；PR 3 = PPh 2 Me，SiX 3 = SiCl 3（10），SiHCl 2（5），描述了SiH 2 Cl（6），SiMeCl 2（11）]。钌配合物的甲硅烷基1 - 6由钌氢化物的反应，来制备的Cp（PR 3）2期RuH，与相应的氯硅烷，ClSiX 3 ; 得到副产物二氢化钌[Cp（PR 3）2 RuH 2 ] Cl。膦的空间需求的增加降低了相应的氢化钌对氯硅烷的反应性。甲硅烷复合物1 - 4与LiAlH 4进行氯化物/氢化物交换，得到相应的钌氢化硅烷基络合物Cp（PPhMe 2）2 RuSiHX 2 [SiHX 2 = SiH 3（7），SiMeH 2（8）]。1与AlMe

  DOI：

  10.1021/om0204235
• 作为产物：
  描述：

  盐酸 、 Cp(PMe3)2RuH 以 乙醚 为溶剂， 以97%的产率得到[Cp(PMe3)2RuH2]Cl
  参考文献：
  名称：

  钌和相关金属的氢化物配合物：Cp（PMe3）2RuH和[Cp（PMe3）2RuH2] BF4的制备和结构

  摘要：

  The reaction of Cp(PMe(3))(2)RuCl with either KOMe in MeOH or LiAlH4 in Et(2)O produces the hydride Cp(PMe(3))(2)RuH (1) in high yield. Protonation of 1 with HX quantitatively generates the dihydrides [Cp(PMe(3))(2)RuH2]X (X = Cl (2), BF4 (3), B[3,5-(CF3)(2)C6H3](4) (4)). The spectroscopic data on 3 indicate a classical dihydride configuration with no evidence for a dihydrogen tautomer. The pK(a) of 3 in CH2Cl2 is 13.9, and the contribution of the ancillary ligands to the pK(a) value is discussed. X-ray crystal structures of hydride 1 and dihydride 3 have been determined. Hydride 1 exhibits a ''three-legged piano stool'' geometry, while the cation of 3 exhibits a ''four-legged piano stool'' geometry, consistent with the classical dihydride configuration. A comparison of the structures of 1 and 3 with related d(6) Cp'L(2)MH, d(4) Cp'L(2)MH(2), and d(6) Cp'L(2)M(eta(2)-H-2) complexes (Cp' = eta(5)-C5H5, eta(5)-C(5)Me(5), eta(5)-C(5)H(5)Me) reveals several general structural trends. First, the angle between the Cp' plane and the ML(2) plane lies in the range 59-79 degrees (mean 67.6(13)degrees) for d(6) CP'L(2)MH complexes but is in the range 86-90 degrees (mean 87.6(4)degrees) for d(4) Cp'L(2)MH(2) complexes and has a mean value of 56.1(8)degrees for known d(6) Cp'L(2)M(eta(2)-H-2) complexes. Second, the angle between the M-H vector and the normal to the ML(2) plane is generally less than 10 degrees (mean 7.9(12)degrees) for the d(6) Cp'L(2)MH complexes, while in d(4) Cp'L(2)MH(2) complexes the M-H vector is shifted toward the ML(2) plane, increasing this angle by ca. 20 degrees (mean 30.0(20)degrees). The corresponding angle in d(6) Cp'L(2)M(eta(2)-H-2) complexes has a mean value of 15.5(18)degrees. Third, the L-M-L' angles in d(6) Cp'L(2)MH complexes (range 84-101 degrees, mean 93.0(19)degrees) are typically smaller that the corresponding angles in d(4) CP'L(2)MH(2) complexes (range 101-111 degrees, mean 107.2(10)degrees).

  DOI：

  10.1021/om00008a051

文献信息

• Ruthenium Silyl Complexes Containing the Cp(PMe₃)₂Ru Moiety:  Preparation, Substituent Effects, and Silylene Character in the Ru−Si Bond
  作者：Frederick R. Lemke、Kevin J. Galat、Wiley J. Youngs

  DOI：10.1021/om980951+

  日期：1999.4.1

  The preparation and characterization of new ruthenium(II) silyl complexes containing the Cp(PM3)2Ru moiety are described. The ruthenium(II) hydride Cp(PMe3)2RuH reacts with a variety of chlorosilanes to produce the ruthenium(II) silyl complexes Cp(PMe3)2RuSiR3 [SiR3 = SiCl3 (1), SiHCl2 (2), SiH2Cl (3), SiMeCl2 (4), SiMeHCl (5), SiMe2Cl (6)] and the ruthenium(IV) dihydride [Cp(PMe3)2RuH2]Cl. Silyl complexes

  描述了含有Cp（PM 3）2 Ru部分的新钌（II）甲硅烷基络合物的制备和表征。氢化钌（II）Cp（PMe 3）2 RuH与多种氯硅烷反应生成钌（II）甲硅烷基络合物Cp（PMe 3）2 RuSiR 3 [SiR 3 = SiCl 3（1），SiHCl 2（2），SiH 2 Cl（3），SiMeCl 2（4），SiMeHCl（5），SiMe 2 Cl（6）]和二氢化钌（IV）[Cp（PMe 3）2 RuH 2 ] Cl。甲硅烷复合物1 - 6经历与的LiAlH氯乙烯/氢化物交换4，得到相应的钌（II）氢化甲硅烷复合物的Cp（PME 3）2 RuSiHR 2 [SiHR 2 =的SiH 3（7），SiMeH 2（8），森2 ħ （9）]。AlMe 3将6甲基化可生成Cp（PMe 3）2 RuSiMe 3（10）。描述了一种回收Cp（PMe 3）2 Ru部分的方法。1的结构通过X射线晶体学确定。配合物1
• (η¹-Pentamethylcyclopentadienyl)silyl Complexes of Ruthenium. Preparation, Reactivity, and X-ray Crystal Structure of Cp(PMe₃)₂RuSiCl₂(η¹-Cp*)
  作者：Frederick R. Lemke、Richard S. Simons、Wiley J. Youngs

  DOI：10.1021/om9504866

  日期：1996.1.9

  of Cp(PMe3)2RuCH2SiMe3 (1) with (η1-Cp*)SiHCl2 in refluxing toluene produces silyl Cp(PMe3)2RuSiCl2(η1-Cp*) (2) in good yields; Cp(PMe3)2RuSiCl3 (3) is a minor product of this reaction. The Cp* group in 2 is σ-bound to the silicon and is “static” on the NMR time scale at room temperature. The η1-Cp* configuration in 2 was confirmed by a single-crystal X-ray diffraction study. In the structure of 2,

  CP的反应（PME 3）2 RUCH 2森达3（1）用（η 1 -CP *）的SiHCl 2中的甲硅烷基的CP（PME产生回流甲苯3）2 RuSiCl 2（η 1 -CP *）（2）在良率；CP（PMe 3）2 RuSiCl 3（3）是该反应的次要产物。在CP *组2是σ键合到硅和是“静态”在NMR时间刻度在室温。在η 1在-CP *配置2通过单晶X射线衍射研究证实。在2的结构中，在钌周围观察到“三足钢琴凳”的几何形状，而硅采用扭曲的四面体几何形状。在η 1上硅-CP *基团是在抗与钌膦中的一个（二面角= 179.5（3）°）的关系。配合物2表现出涉及氯化物取代，Si-CP *键断裂和Ru-Si键断裂的反应。的反应2用的LiAlH 4产生的CP（PME 3）2 RuSiH 2（η 1 -CP *）（6），其中η 1-CP *组比2更具移动性。在Si-的CP *的键2通过酸易于切割（我。Ë
• The Chloride Effect:  Structural Dependence of Ruthenium Silyl Complexes on Phosphorus and Silicon Substituents
  作者：Samuel T. N. Freeman、Jeffrey L. Petersen、Fredrick R. Lemke

  DOI：10.1021/om034226x

  日期：2004.3.1

  The structures for a series of Cp(PR3)(2),RuSiX3 PR3 = PMe3, SiX3 = SiCl3, SiMeCl2, SiPhCl2; PR3 = PMe2Ph, SiX3 = SiCl3} complexes were determined and compared. The Ru-Si and Si-Cl distances in these complexes increased when Cl was replaced with Me or Ph groups and correlated with the observed spectroscopic properties of these complexes. The structural variations were explained by d(Ru)-sigma*(Si-Cl) pi-back-bonding interactions.