OsH3(pyrazole)(pyrazolate)(triisopropylphosphine)2 | 184014-59-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: OsH3(pyrazole)(pyrazolate)(triisopropylphosphine)2
• CAS: 184014-59-3
• 化学式: C₂₄H₅₂N₄OsP₂
• 分子量: 648.851
• InChiKey: RFEYGQQWEQVXSV-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：
  None
• 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：

  tetrafluoroboric acid 、 OsH3(pyrazole)(pyrazolate)(triisopropylphosphine)2 以 乙醚 为溶剂， 以90%的产率得到[OsH3(pyrazole)2(triisopropylphosphine)2]BF4
  参考文献：
  名称：

  Quantum Mechanical Exchange Coupling in Trihydridoosmium Complexes Containing Azole Ligands

  摘要：

  The reaction of the hexahydrido complex OsH6(PiPr(3))(2) (1) with 2,2'-biimiazole (H(2)biim) leads to the trihydrido complex OsH3(Hbiim)((PPr3)-Pr-i)(2) (2). Complex 2 reacts with the dimers [M(mu-OMe)(COD)](2) (COD = 1,5-cyclooctadiene) to afford the heterobimetallic derivatives ((PPr3)-Pr-i)(2)H3Os(mu-biim)M(COD) (M = Rh (3), Ir (4)). The structure of 4 was determined by an X-ray investigation. Complex 4 crystallizes in the triclinic space group (No. 2) with a = 8.978(2) Angstrom, b = 13.629(3) Angstrom, c = 15.369(3) Angstrom, alpha = 79.34(2)degrees, beta = 86.31(2)degrees, gamma = 72.43(1)degrees, and Z = 2. The coordination geometry around the osmium atom can be described as a distorted pentagonal bipyramid with the two phosphorus atoms of the phosphine ligands occupying trans positions. The osmium coordination sphere is completed by the hydride ligands and by the chelating Ir(biim)(COD) group, bonded through two nitrogen atoms. The H-H separations are 1.57(5) and 1.59(7) Angstrom. Complex 1 also reacts with pyrazole (Hpz). The reaction gives OsH3(pz)(Hpz)((PPr3)-Pr-i)(2) (5), which affords [OsH3(Hpz)(2)((PPr3)-Pr-i)(2)]BF4 (6) and OsH3Cl(Hpz)((PPr3)-Pr-i)(2) (7) by reaction with HBF4 and HCl, respectively. The H-1 NMR spectra of 2-4 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 JA-M are abnormally large (between 31.7 and 76.0 Hz) and temperature dependent. Furthermore, they are inversely proportional to the electron density on the osmium atom, increasing in the sequence 2 < 3 < 4. These results are interpreted in terms of the operation of quantum mechanical coupling between the hydrogen nuclei in the OsH3 unit.

  DOI：

  10.1021/ic960446+
• 作为产物：
  描述：

  吡唑 、 bis(triisopropylphosphane)(dihydrido)dichloroosmium(IV) 、 sodium tetrahydroborate 以 甲苯 为溶剂， 以85%的产率得到OsH3(pyrazole)(pyrazolate)(triisopropylphosphine)2
  参考文献：
  名称：

  Quantum Mechanical Exchange Coupling in Trihydridoosmium Complexes Containing Azole Ligands

  摘要：

  The reaction of the hexahydrido complex OsH6(PiPr(3))(2) (1) with 2,2'-biimiazole (H(2)biim) leads to the trihydrido complex OsH3(Hbiim)((PPr3)-Pr-i)(2) (2). Complex 2 reacts with the dimers [M(mu-OMe)(COD)](2) (COD = 1,5-cyclooctadiene) to afford the heterobimetallic derivatives ((PPr3)-Pr-i)(2)H3Os(mu-biim)M(COD) (M = Rh (3), Ir (4)). The structure of 4 was determined by an X-ray investigation. Complex 4 crystallizes in the triclinic space group (No. 2) with a = 8.978(2) Angstrom, b = 13.629(3) Angstrom, c = 15.369(3) Angstrom, alpha = 79.34(2)degrees, beta = 86.31(2)degrees, gamma = 72.43(1)degrees, and Z = 2. The coordination geometry around the osmium atom can be described as a distorted pentagonal bipyramid with the two phosphorus atoms of the phosphine ligands occupying trans positions. The osmium coordination sphere is completed by the hydride ligands and by the chelating Ir(biim)(COD) group, bonded through two nitrogen atoms. The H-H separations are 1.57(5) and 1.59(7) Angstrom. Complex 1 also reacts with pyrazole (Hpz). The reaction gives OsH3(pz)(Hpz)((PPr3)-Pr-i)(2) (5), which affords [OsH3(Hpz)(2)((PPr3)-Pr-i)(2)]BF4 (6) and OsH3Cl(Hpz)((PPr3)-Pr-i)(2) (7) by reaction with HBF4 and HCl, respectively. The H-1 NMR spectra of 2-4 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 JA-M are abnormally large (between 31.7 and 76.0 Hz) and temperature dependent. Furthermore, they are inversely proportional to the electron density on the osmium atom, increasing in the sequence 2 < 3 < 4. These results are interpreted in terms of the operation of quantum mechanical coupling between the hydrogen nuclei in the OsH3 unit.

  DOI：

  10.1021/ic960446+