[OsH(κ2-O2CCH3)(CCH=CPh2)(P(i-Pr)3)2]BF4 | 936073-49-3

• 英文名称: [OsH(κ2-O2CCH3)(CCH=CPh2)(P(i-Pr)3)2]BF4
• CAS: 936073-49-3
• 化学式: BF₄*C₃₅H₅₇O₂OsP₂
• 分子量: 848.789
• InChiKey: YPPIVBBDARYJNC-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：

  氘代乙腈 、 [OsH(κ2-O2CCH3)(CCH=CPh2)(P(i-Pr)3)2]BF4 以 氘代乙腈 为溶剂， 生成 [OsH(κ1-O2CCH3)(CD3CN)(CCH=CPh2)(P(i-Pr)3)2]BF4
  参考文献：
  名称：

  Hydride-Carbyne to Carbene Transformation in an Osmium-Acetate-Bis(triisopropylphosphine) System:  Influence of the Coordination Mode of the Carboxylate and the Reaction Solvent

  摘要：

  The bis-solvato hydride-allenylidene complex [OsH(CCCPh2)(CH3CN)(2)((PPr3)-Pr-i)(2)]BF4 (1) reacts with acetic acid to give the hydride-carbyne [OsH(kappa(2)-O2CCH3)(CCHCPh2)((PPr3)-Pr-i)(2)]BF4 (2), which in 1,2-dichloroethane under reflux is stable and does not evolve into its five-coordinate carbene isomer. In acetonitrile at room temperature, complex 2 is in equilibrium with [OsH{kappa(1)-OC(O)CH3}(CCHCPh2)(CH3CN)((PPr3)-Pr-i)(2)]BF4 (4; Delta H degrees = -6.4 +/- 0.3 kcal center dot mol(-1), Delta S degrees = -22.9 +/- 1.1 eu). At 353 K, complex 4 is transformed into the carbene [Os{kappa(1)-OC(O)CH3}(CHCHCPh2)(CH3CN)(2)((PPr3)-Pr-i)(2)]BF4 (5; 40%), which is obtained in high yield (88%) by reaction of [Os(CHCHCPh2)(CH3CN)(3)((PPr3)-Pr-i)(2)][BF4](2) with sodium acetate in 2-propanol. The hydride-carbyne to carbene transformation is analyzed by DFT calculations.

  DOI：

  10.1021/om0611655
• 作为产物：
  描述：

  溶剂黄146 、 [OsH(=C=C=CPh2)(CH3CN)2(P(i-Pr)3)2]BF4 以 二氯甲烷 、 溶剂黄146 为溶剂， 以93%的产率得到[OsH(κ2-O2CCH3)(CCH=CPh2)(P(i-Pr)3)2]BF4
  参考文献：
  名称：

  Hydride-Carbyne to Carbene Transformation in an Osmium-Acetate-Bis(triisopropylphosphine) System:  Influence of the Coordination Mode of the Carboxylate and the Reaction Solvent

  摘要：

  The bis-solvato hydride-allenylidene complex [OsH(CCCPh2)(CH3CN)(2)((PPr3)-Pr-i)(2)]BF4 (1) reacts with acetic acid to give the hydride-carbyne [OsH(kappa(2)-O2CCH3)(CCHCPh2)((PPr3)-Pr-i)(2)]BF4 (2), which in 1,2-dichloroethane under reflux is stable and does not evolve into its five-coordinate carbene isomer. In acetonitrile at room temperature, complex 2 is in equilibrium with [OsH{kappa(1)-OC(O)CH3}(CCHCPh2)(CH3CN)((PPr3)-Pr-i)(2)]BF4 (4; Delta H degrees = -6.4 +/- 0.3 kcal center dot mol(-1), Delta S degrees = -22.9 +/- 1.1 eu). At 353 K, complex 4 is transformed into the carbene [Os{kappa(1)-OC(O)CH3}(CHCHCPh2)(CH3CN)(2)((PPr3)-Pr-i)(2)]BF4 (5; 40%), which is obtained in high yield (88%) by reaction of [Os(CHCHCPh2)(CH3CN)(3)((PPr3)-Pr-i)(2)][BF4](2) with sodium acetate in 2-propanol. The hydride-carbyne to carbene transformation is analyzed by DFT calculations.

  DOI：

  10.1021/om0611655