[Cp*RuH(CCC(OH)HPh)(PMe(i)Pr2)2][B(3,5-C6H3(CF3)2)4] | 543728-76-3

• 英文名称: [Cp*RuH(CCC(OH)HPh)(PMe(i)Pr2)2][B(3,5-C6H3(CF3)2)4]
• CAS: 543728-76-3
• 化学式: C₃₂H₁₂BF₂₄*C₃₃H₅₇OP₂Ru
• 分子量: 1496.05
• InChiKey: IJVLQDSYEHIQMO-WXUYGYNPSA-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：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [Cp*RuH(CCC(OH)HPh)(PMe(i)Pr2)2][B(3,5-C6H3(CF3)2)4] 以 neat (no solvent) 为溶剂， 以99%的产率得到[Cp*Ru(=C=CHC(OH)HPh)(PMe(i)Pr2)2][B(3,5-C6H3(CF3)2)4]
  参考文献：
  名称：

  Structure and Dynamics of Half-Sandwich Ruthenium(IV) Alkynyl Hydrido Complexes

  摘要：

  The coordinatively unsaturated complex [Cp*Ru((PMePr2)-Pr-i)(2)][BAr'(4)] (1; BAr'(4) = B{3,5-C6H3(CF3)(2)}(4)) reacts with 1-alkynes in diethyl ether at 0 degreesC, furnishing the Ru-IV alkynyl hydrido derivatives [Cp*RuH(Cequivalent toCR)((PMePr2)-Pr-i)(2)] [BAr'(4)]. In an analogous fashion, the reaction of I with 1-alkyn-3-ols in diethyl ether at 0 degreesC leads to the 3-hydroxyalkynyl hydrido complexes [Cp*RuH(Cequivalent toCC(OH)RR')((PMePr2)-Pr-i)(2)][BAr'(4)]. The complexes [Cp*RuH(Cequivalent toCCOOMe)((PMePr2)-Pr-i)(2)][BAr'(4)] and [Cp*RuH(Cequivalent toCC(OH)Ph-2)((PMePr2)-Pr-i)(2)][BAr'(4)].Et2O have been structurally characterized, and their crystal structures show a transoid disposition of the hydride and alkynyl ligands. These compounds are stereochemically nonrigid and undergo a rapid equilibrium between possible stereoisomers in solution, which has been studied by variable-temperature NMR spectroscopy and computer simulation. The dynamic NMR study for these processes indicates energy barriers of ca. 11 kcal mol(-1), and moreover the differences in energy for the possible stereoisomers are very small (ca. 1 kcal mol(-1)). The alkynyl hydrido complexes rearrange to their more stable vinylidene or hydroxyvinylidene, tautomers. Spontaneous dehydration of the latter leads to either vinylvinylidene or allenylidene complexes.

  DOI：

  10.1021/om020940n
• 作为产物：
  描述：

  [(pentamethylcyclopentadienyl)Ru(P(i-Pr)2Me)2][B(3,5-(CF3)2C6H3)4] 、 (+/-)-1-苯基-2-丙炔-1-醇 以 二氯甲烷 为溶剂， 生成 [Cp*RuH(CCC(OH)HPh)(PMe(i)Pr2)2][B(3,5-C6H3(CF3)2)4]
  参考文献：
  名称：

  Structure and Dynamics of Half-Sandwich Ruthenium(IV) Alkynyl Hydrido Complexes

  摘要：

  The coordinatively unsaturated complex [Cp*Ru((PMePr2)-Pr-i)(2)][BAr'(4)] (1; BAr'(4) = B{3,5-C6H3(CF3)(2)}(4)) reacts with 1-alkynes in diethyl ether at 0 degreesC, furnishing the Ru-IV alkynyl hydrido derivatives [Cp*RuH(Cequivalent toCR)((PMePr2)-Pr-i)(2)] [BAr'(4)]. In an analogous fashion, the reaction of I with 1-alkyn-3-ols in diethyl ether at 0 degreesC leads to the 3-hydroxyalkynyl hydrido complexes [Cp*RuH(Cequivalent toCC(OH)RR')((PMePr2)-Pr-i)(2)][BAr'(4)]. The complexes [Cp*RuH(Cequivalent toCCOOMe)((PMePr2)-Pr-i)(2)][BAr'(4)] and [Cp*RuH(Cequivalent toCC(OH)Ph-2)((PMePr2)-Pr-i)(2)][BAr'(4)].Et2O have been structurally characterized, and their crystal structures show a transoid disposition of the hydride and alkynyl ligands. These compounds are stereochemically nonrigid and undergo a rapid equilibrium between possible stereoisomers in solution, which has been studied by variable-temperature NMR spectroscopy and computer simulation. The dynamic NMR study for these processes indicates energy barriers of ca. 11 kcal mol(-1), and moreover the differences in energy for the possible stereoisomers are very small (ca. 1 kcal mol(-1)). The alkynyl hydrido complexes rearrange to their more stable vinylidene or hydroxyvinylidene, tautomers. Spontaneous dehydration of the latter leads to either vinylvinylidene or allenylidene complexes.

  DOI：

  10.1021/om020940n