OsH2(η(4)-1,3-cyclohexadiene)[P(isopropyl)3]2 | 196213-14-6

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: OsH2(η(4)-1,3-cyclohexadiene)[P(isopropyl)3]2
• 英文别名: cyclohexa-1,3-diene;osmium dihydride;tri(propan-2-yl)phosphane
• CAS: 196213-14-6
• 化学式: C₂₄H₅₂OsP₂
• 分子量: 592.824
• InChiKey: VHNNFBPFOJRYTM-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：

  tetrafluoroboric acid 、 OsH2(η(4)-1,3-cyclohexadiene)[P(isopropyl)3]2 以 乙醚 为溶剂， 以85%的产率得到[OsH2(η(3)-C6H9)(P(isopropyl)3)2]BF4
  参考文献：
  名称：

  Dihydrido and Trihydrido Diolefin Complexes Stabilized by the Os(PiPr₃)₂ Unit:  New Examples of Quantum Mechanical Exchange Coupling in Trihydrido Osmium Compounds

  摘要：

  The hexahydrido complex OsH6(PiPr(3))2 (1) reacts with tetrafluorobenzobarrelene (TFB), 2,5-norbornadiene (NBD), and 1,3-cyclohexadiene to afford OsH2(eta(4)-TFB)(PiPr(3))(2) (2), OsH2(eta(4)-NBD)(PiPr(3))(2) (3), and OsH2(eta(4)-cyclohexadiene)(PiPr(3))(2) (4), respectively. The protonation of 2 and 3 with HBF4 yields [OsH3(eta(4)-TFB)(PiPr(3))(2)]BF4 (5) and [OsH3(eta(4)-NBD)(PiPr(3))(2)]BF4 (6) The H-1 NMR spectra of 5 and 6 in the hydride region at low temperature display AM(2)X(2) spin systems (X = P-31), which are simplified to AM(2) spin systems in the H-1{P-31} spectra. The values for J(AM) are temperature dependent, increasing from 13.1 to 35.9 Hz (5) and from 11.0 to 17.7 Hz (6) as temperature is increased from 190 to 230 K and from 180 to 240 K, respectively. The reaction of 4 with HBF4 leads to the cyclohexenyl complex [OsH2(eta(3)-C6H9)(PiPr(3))(2)]BF4 (7), which shows an agostic interaction between the osmium center and one of the two endo-CH bonds adjacent to the pi-allyl unit. In solution complex 7 is fluxional. The fluxional process involves the exchange between the relative positions of the hydride ligands and the endo-CH hydrogen atoms of the cyclohexenyl ligand and, at the same time, the exchange between the CH allyl and the exo-CH hydrogen atoms inside the cyclohexenyl ligand. The structure of 7 in the solid state has been determined by X-ray diffraction. The distribution of ligands around the osmium atom can be described as a piano stool geometry with the agostic hydrogen atom and the midpoints of the carbon-carbon bonds involved in the pi-allyl unit forming the three-membered face, while both the hydride and phosphine ligands lie in the four-membered face.

  DOI：

  10.1021/ja9700212
• 作为产物：
  描述：

  Os(hydride)6(triisopropylphosphine)2 、 1,3-环己二烯 以 甲苯 为溶剂， 以78%的产率得到OsH2(η(4)-1,3-cyclohexadiene)[P(isopropyl)3]2
  参考文献：
  名称：

  Dihydrido and Trihydrido Diolefin Complexes Stabilized by the Os(PiPr₃)₂ Unit:  New Examples of Quantum Mechanical Exchange Coupling in Trihydrido Osmium Compounds

  摘要：

  The hexahydrido complex OsH6(PiPr(3))2 (1) reacts with tetrafluorobenzobarrelene (TFB), 2,5-norbornadiene (NBD), and 1,3-cyclohexadiene to afford OsH2(eta(4)-TFB)(PiPr(3))(2) (2), OsH2(eta(4)-NBD)(PiPr(3))(2) (3), and OsH2(eta(4)-cyclohexadiene)(PiPr(3))(2) (4), respectively. The protonation of 2 and 3 with HBF4 yields [OsH3(eta(4)-TFB)(PiPr(3))(2)]BF4 (5) and [OsH3(eta(4)-NBD)(PiPr(3))(2)]BF4 (6) The H-1 NMR spectra of 5 and 6 in the hydride region at low temperature display AM(2)X(2) spin systems (X = P-31), which are simplified to AM(2) spin systems in the H-1{P-31} spectra. The values for J(AM) are temperature dependent, increasing from 13.1 to 35.9 Hz (5) and from 11.0 to 17.7 Hz (6) as temperature is increased from 190 to 230 K and from 180 to 240 K, respectively. The reaction of 4 with HBF4 leads to the cyclohexenyl complex [OsH2(eta(3)-C6H9)(PiPr(3))(2)]BF4 (7), which shows an agostic interaction between the osmium center and one of the two endo-CH bonds adjacent to the pi-allyl unit. In solution complex 7 is fluxional. The fluxional process involves the exchange between the relative positions of the hydride ligands and the endo-CH hydrogen atoms of the cyclohexenyl ligand and, at the same time, the exchange between the CH allyl and the exo-CH hydrogen atoms inside the cyclohexenyl ligand. The structure of 7 in the solid state has been determined by X-ray diffraction. The distribution of ligands around the osmium atom can be described as a piano stool geometry with the agostic hydrogen atom and the midpoints of the carbon-carbon bonds involved in the pi-allyl unit forming the three-membered face, while both the hydride and phosphine ligands lie in the four-membered face.

  DOI：

  10.1021/ja9700212