[RuH2(η2-H2)(η2-HBpin)(PCy3)2] | 856908-05-9

• 英文名称: [RuH2(η2-H2)(η2-HBpin)(PCy3)2]
• 英文别名: [RuH2(η2-H2)(η2-HB(OCMe2)2)(tricyclohexylphosphine)2]；RuH2(σ-H2)(σ-pinacolborane)(PCy3)2
• CAS: 856908-05-9
• 化学式: C₄₂H₈₃BO₂P₂Ru
• 分子量: 793.948
• InChiKey: UALRYQKLUFMCFM-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：

  [RuH2(η2-H2)(η2-HBpin)(PCy3)2] 、 氢气 以 not given 为溶剂， 生成 RuH2(H2)2(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
• 作为产物：
  描述：

  [RuH((μ-H)2B(OCMe2)2)(η2-HB(OCMe2)2)(tricyclohexylphosphine)2] 、 氢气 以 氘代甲苯 为溶剂， 生成 [RuH2(η2-H2)(η2-HBpin)(PCy3)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

文献信息

• 9-BBN activation. Synthesis, crystal structure and theoretical characterization of the ruthenium complex Ru[(μ-H)2BC8H14]2(PCy3)
  作者：Khaled Essalah、Jean-Claude Barthelat、Virginia Montiel、Sébastien Lachaize、Bruno Donnadieu、Bruno Chaudret、Sylviane Sabo-Etienne

  DOI：10.1016/s0022-328x(03)00343-7

  日期：2003.8

  Reaction of the bis(dihydrogen) ruthenium complex RuH2(H-2)(2)(PCy3)(2) (1) with an excess of 9-borabicyclononane yields Ru[(mu-H)(2)BC8H14](2)(PCy3) (6) and the phosphine adduct (PCy3HBC8H14)-H-.. The new complex is characterized by NMR spectroscopy and X-ray diffraction. New X-ray data on 9-BBN dimer, from a measurement at 180 K, are also reported. DFT calculations (B3LYP) on Ru[(mu-H)(2)BC8H14](2)(PMe3) (7), the PMe3 analogue of 6, confirm the ruthenium (II) formulation with two dihydroborate ligands. The data obtained using PH3 or PMe3 as models for PCy3 in (PR3HBC8H14)-H-. are also discussed. (C) 2003 Elsevier Science B.V. All rights reserved.