(Cp*Ru)₃{μ₃-η²:η²(⊥)-propyne}(μ-H)₃ | 1416143-78-6

• 英文名称: (Cp*Ru)₃{μ₃-η²:η²(⊥)-propyne}(μ-H)₃
• CAS: 1416143-78-6
• 化学式: C₃₃H₅₂Ru₃
• 分子量: 751.986
• InChiKey: BRCRHMCWHDESHJ-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  (Cp*Ru)₃{μ₃-η²:η²(⊥)-propyne}(μ-H)₃ 以 正庚烷 为溶剂， 反应 3.0h， 生成 (Cp*Ru)₃{μ₃-η²(∥)-CHCH}(μ₃-methylidyne)(μ-H)₂ 、 (Cp*Ru)₃{μ₃-η²(∥)-vinyl}(μ₃-methylidyne)(μ-H)
  参考文献：
  名称：

  Synthesis and Dynamic Properties of a Triruthenium Complex Containing μ₃-η²(∥)-Ethyne and μ₃-Methylidyne Ligands: Equilibrium of an Ethyne–Hydrido Complex with a Nonclassical μ₃-Vinyl Complex

  摘要：

  A triruthenium complex containing mu(3)-eta(2)(parallel to)-ethyne and mu(3)-methylidyne ligands, (CpRu)(3){mu(3)-eta(2)(parallel to)-HC CH}(mu(3)-CH)(mu-H)(2) (2a), was synthesized via the treatment of {Cp*Ru(mu-H)}(3)(mu(3)-H)(2) (3) (Cp* = eta(5)-C5Me5) with propene. In the low-temperature region, VT H-1 NMR spectra showed that complex 2a is in equilibrium with a nonclassical mu(3)-vinyl complex, (CpRu)(3)(mu(3)-eta(2):eta(2)-HC=CH2)(mu(3)-CH)(mu-H) (5a), which features an interaction between one of the beta-vinyl protons and a Ru center. The presence of the unusual 3c-2e interaction of the beta-C-H bond of the vinyl group is strongly supported by the small J(C-H) value (98 Hz) found for the beta-carbon as well as the small J(H-H) value for the a-vinyl proton. Treatment of the equilibrated mixture of phenyl-substituted complexes (CpRu)(3){mu(3)-eta(2)(parallel to)-HC CPh}(mu(3)-CH)(mu-H)(2) (2b) and (CpRu)(3)(mu(3)-eta(2):eta(2)-HC=CHPh)(mu(3)-CH)(mu-H) (5b) with tBuNC afforded a mu-styryl complex, (CpRu)(3)(mu-eta(2)-HC=CHPh)(mu(3)-CH)(mu-tBuNC)(mu-H) (6), while analogous treatment of 2a and 5a resulted in the formation of mu(3)-dimetalloallyl complex (CpRu)(3){mu(3)-eta(3)-CHCHCN(H)tBu}(mu(3)-CH)(mu-H) (7). These results imply that the coordinatively saturated mu(3)-eta(2)(parallel to)-alkyne-mu(3)-alkylidyne complex can generate a vacant site via the migration of a hydrido ligand onto an alkyne ligand to yield a mu-vinyl intermediate.

  DOI：

  10.1021/om301064y
• 作为产物：
  描述：

  三聚丙烯 、 [((η5-pentamethylcyclopentadienyl)Ru)3(μ-hydrido)3(μ3-hydrido)2] 以 甲苯 为溶剂， 25.0~80.0 ℃ 、101.33 kPa 条件下， 反应 48.0h， 以71%的产率得到(Cp*Ru)₃{μ₃-η²:η²(⊥)-propyne}(μ-H)₃
  参考文献：
  名称：

  Synthesis and Dynamic Properties of a Triruthenium Complex Containing μ₃-η²(∥)-Ethyne and μ₃-Methylidyne Ligands: Equilibrium of an Ethyne–Hydrido Complex with a Nonclassical μ₃-Vinyl Complex

  摘要：

  A triruthenium complex containing mu(3)-eta(2)(parallel to)-ethyne and mu(3)-methylidyne ligands, (CpRu)(3){mu(3)-eta(2)(parallel to)-HC CH}(mu(3)-CH)(mu-H)(2) (2a), was synthesized via the treatment of {Cp*Ru(mu-H)}(3)(mu(3)-H)(2) (3) (Cp* = eta(5)-C5Me5) with propene. In the low-temperature region, VT H-1 NMR spectra showed that complex 2a is in equilibrium with a nonclassical mu(3)-vinyl complex, (CpRu)(3)(mu(3)-eta(2):eta(2)-HC=CH2)(mu(3)-CH)(mu-H) (5a), which features an interaction between one of the beta-vinyl protons and a Ru center. The presence of the unusual 3c-2e interaction of the beta-C-H bond of the vinyl group is strongly supported by the small J(C-H) value (98 Hz) found for the beta-carbon as well as the small J(H-H) value for the a-vinyl proton. Treatment of the equilibrated mixture of phenyl-substituted complexes (CpRu)(3){mu(3)-eta(2)(parallel to)-HC CPh}(mu(3)-CH)(mu-H)(2) (2b) and (CpRu)(3)(mu(3)-eta(2):eta(2)-HC=CHPh)(mu(3)-CH)(mu-H) (5b) with tBuNC afforded a mu-styryl complex, (CpRu)(3)(mu-eta(2)-HC=CHPh)(mu(3)-CH)(mu-tBuNC)(mu-H) (6), while analogous treatment of 2a and 5a resulted in the formation of mu(3)-dimetalloallyl complex (CpRu)(3){mu(3)-eta(3)-CHCHCN(H)tBu}(mu(3)-CH)(mu-H) (7). These results imply that the coordinatively saturated mu(3)-eta(2)(parallel to)-alkyne-mu(3)-alkylidyne complex can generate a vacant site via the migration of a hydrido ligand onto an alkyne ligand to yield a mu-vinyl intermediate.

  DOI：

  10.1021/om301064y