[RuH2(η2-H2)(η2-HBOC6H4O)(tricyclohexylphosphine)2] | 856908-06-0

• 英文名称: [RuH2(η2-H2)(η2-HBOC6H4O)(tricyclohexylphosphine)2]
• 英文别名: [RuH2(η2-H2(η2-HBcat)(PCy3)2]
• CAS: 856908-06-0
• 化学式: C₄₂H₇₅BO₂P₂Ru
• 分子量: 785.885
• InChiKey: DSVKWVCRPPNWHF-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：

  [RuH2(η2-H2)(η2-HBOC6H4O)(tricyclohexylphosphine)2] 、 儿萘酚硼烷 以 not given 为溶剂， 生成 [RuH(η6-C6H4O2BO2C6H4)(triphenylphosphine)2]
  参考文献：
  名称：

  Coordination Modes of Boranes in Polyhydride Ruthenium Complexes:  σ-Borane versus Dihydridoborate

  摘要：

  The bis(dihydrogen) complex RuH2(eta(2)-H-2)(2)(PCy3)(2) (1) reacts at room temperature with 1 equiv of either HBpin or HBcat to produce the a-borane complexes RuH2(eta(2)-HBpin)(eta(2)-H-2)(PCy3)(2) (2Bpin) and RuH2(eta(2)-HBcat)(eta(2)-H-2)(PCy3)(2) (2Bcat), respectively, by substitution of one sigma-H-2 ligand by one sigma-B-H. In contrast, when using the 9-BBN reagent, the dihydridoborate complex RuH[(mu-H)(2)BBN](eta(2)-H-2)(PCy3)(2) (2BBN) is formed. The coordination modes of the borane ligands have been ascertained by NMR spectroscopy, X-ray diffraction, and theoretical studies (DFT/B3LYP). The results indicate that the dialkoxyborane ligands (HBpin and HBcat) are not acidic enough to stabilize a "true" symmetrical dihydridoborate coordination mode. They thus lead to a-borane complexes presenting a small H/BH cis interaction between the boron atom and the adjacent hydride. The sigma-H-2 ligand in 2Bpin is located by X-ray diffraction at 90 K and found to be perpendicular to the equatorial plane. DFT calculations lead to the optimization of the two degenerate isomers RuH2[eta(2)-HB(OCH2)(2)](eta(2)-H-2)(PMe3)(2) (5Bpin_a) (analogous to 2Bpin) and RuH[(mu-H)(2)B(OCH2)(2)](eta(2)-H-2)(PMe3)(2) (5Bpin_b), demonstrating that sigma-H-2 rotation and sigma-borane versus dihydridoborate ligation are intimately correlated. In contrast, the 9-BBN reagent is a strong Lewis acid and leads to a dihydridoborate complex. The theoretical study on RuH[(mu-H)(2)Bpin](eta(2)-HBpin)(PCy3)(2) (3Bpin) shows that the bonding is also dependent on the hydride basicity: the RuH[(mu-H)(2)B(OCH2)(2)](PMe3)(2) fragment used as a model for RuH[(mu-H)2Bpin](PCy3)2 is not basic enough to contain a second ligand bound in a dihydridoborate mode, despite the stabilization that should be gained from the resulting symmetrical structure.

  DOI：

  10.1021/om050276l
• 作为产物：
  描述：

  RuH2(H2)2(tricyclohexylphosphine)2 、 儿萘酚硼烷 以 正戊烷 为溶剂， 以32%的产率得到[RuH2(η2-H2)(η2-HBOC6H4O)(tricyclohexylphosphine)2]
  参考文献：
  名称：

  Coordination Modes of Boranes in Polyhydride Ruthenium Complexes:  σ-Borane versus Dihydridoborate

  摘要：

  The bis(dihydrogen) complex RuH2(eta(2)-H-2)(2)(PCy3)(2) (1) reacts at room temperature with 1 equiv of either HBpin or HBcat to produce the a-borane complexes RuH2(eta(2)-HBpin)(eta(2)-H-2)(PCy3)(2) (2Bpin) and RuH2(eta(2)-HBcat)(eta(2)-H-2)(PCy3)(2) (2Bcat), respectively, by substitution of one sigma-H-2 ligand by one sigma-B-H. In contrast, when using the 9-BBN reagent, the dihydridoborate complex RuH[(mu-H)(2)BBN](eta(2)-H-2)(PCy3)(2) (2BBN) is formed. The coordination modes of the borane ligands have been ascertained by NMR spectroscopy, X-ray diffraction, and theoretical studies (DFT/B3LYP). The results indicate that the dialkoxyborane ligands (HBpin and HBcat) are not acidic enough to stabilize a "true" symmetrical dihydridoborate coordination mode. They thus lead to a-borane complexes presenting a small H/BH cis interaction between the boron atom and the adjacent hydride. The sigma-H-2 ligand in 2Bpin is located by X-ray diffraction at 90 K and found to be perpendicular to the equatorial plane. DFT calculations lead to the optimization of the two degenerate isomers RuH2[eta(2)-HB(OCH2)(2)](eta(2)-H-2)(PMe3)(2) (5Bpin_a) (analogous to 2Bpin) and RuH[(mu-H)(2)B(OCH2)(2)](eta(2)-H-2)(PMe3)(2) (5Bpin_b), demonstrating that sigma-H-2 rotation and sigma-borane versus dihydridoborate ligation are intimately correlated. In contrast, the 9-BBN reagent is a strong Lewis acid and leads to a dihydridoborate complex. The theoretical study on RuH[(mu-H)(2)Bpin](eta(2)-HBpin)(PCy3)(2) (3Bpin) shows that the bonding is also dependent on the hydride basicity: the RuH[(mu-H)(2)B(OCH2)(2)](PMe3)(2) fragment used as a model for RuH[(mu-H)2Bpin](PCy3)2 is not basic enough to contain a second ligand bound in a dihydridoborate mode, despite the stabilization that should be gained from the resulting symmetrical structure.

  DOI：

  10.1021/om050276l