acetonitrile;di(propan-2-yl)-propan-2-ylphosphane;osmium(2+);tri(propan-2-yl)phosphane;tetrafluoroborate | 946166-15-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: acetonitrile;di(propan-2-yl)-propan-2-ylphosphane;osmium(2+);tri(propan-2-yl)phosphane;tetrafluoroborate
• CAS: 946166-15-0
• 化学式: BF₄*C₂₄H₅₀N₃OsP₂
• 分子量: 719.633
• InChiKey: YCPHOMNNRVBYHZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.09
• 重原子数：
  35
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  71.4
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  [OsH(=CHCH=CPh2)(CH3CN)2(P(i-Pr)3)2]BF4 、 乙腈 以 乙腈 为溶剂， 以83%的产率得到acetonitrile;di(propan-2-yl)-propan-2-ylphosphane;osmium(2+);tri(propan-2-yl)phosphane;tetrafluoroborate
  参考文献：
  名称：

  Sequential and Selective Hydrogenation of the C_α−C_β and M−C_α Double Bonds of an Allenylidene Ligand Coordinated to Osmium:  New Reaction Patterns between an Allenylidene Complex and Alcohols

  摘要：

  Complex [OsH(CCCPh2)(CH3CN)(2)((PPr3)-Pr-i)(2)]BF4 (1) reacts with primary and secondary alcohols to give the corresponding dehydrogenated alcohols and the hydride-carbene derivative [OsH(CHCHCPh2)(CH3CN)(2)((PPr3)-Pr-i)(2)]BF4 (2), as a result of hydrogen transfer reactions from the alcohols to the C-alpha-C-beta double bond of the allenylidene ligand of 1. The reactions with phenol and t-butanol, which do not contain any beta-hydrogen, afford the alkoxy-hydride-carbyne complexes [OsH(OR)(CCHCPh2)(CH3CN)((PPr3)-Pr-i)(2)]BF4 (R = Ph (3), Bu-t (4), as a consequence of the 1,3-addition of the O-H bond of the alcohols to the metallic center and the C-beta atom of the allenylidene of 1. On the basis of the reactions of 1 with these tertiary alcohols, deuterium labeling experiments, and DFT calculations, the mechanism of the hydrogenation is proposed. In acetonitrile under reflux, the Os-C double bond of 2 undergoes hydrogenation to give 1,1-diphenylpropene Os{CH2CH(CH3)PPr2(CH3CN)(3)((PPr3)-Pr-i)]BF4 (11), containing a metalated phosphine ligand. This reaction is a first-order process with activation parameters of Delta H = 89.0 +/- 6.3 kJ mol(-1) and Delta S = -43.5 +/- 9.6 J mol(-1) K-1. The X-ray structures of 2 and 3 are also reported.

  DOI：

  10.1021/ja071972a