[Os(C6H4C(O)CH3)(η2-H2)(η1-(CH3)2CO)(P(i)Pr3)2]BF4 | 717875-39-3

• 英文名称: [Os(C6H4C(O)CH3)(η2-H2)(η1-(CH3)2CO)(P(i)Pr3)2]BF4
• CAS: 717875-39-3
• 化学式: BF₄*C₂₉H₅₇O₂OsP₂
• 分子量: 776.723
• InChiKey: LBZQSJASUHHBDT-UHFFFAOYSA-N

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：

  [Os(C6H4C(O)CH3)(η2-H2)(η1-(CH3)2CO)(P(i)Pr3)2]BF4 、 sodium chloride 以 甲醇 为溶剂， 以76%的产率得到[Os(C6H4C(O)CH3)Cl(η2-H2)(P(i)Pr3)2]
  参考文献：
  名称：

  Influence of the Cis Ligand on the H−H Separation and the Rotation Barrier of the Dihydrogen in Osmium-Elongated Dihydrogen Complexes Containing an Ortho-Metalated Ketone

  摘要：

  Treatment of the complex OsH3{C6H4C(O)CH3}((PPr3)-Pr-i)(2) (1) with HBF4.OEt2 in diethyl ether-acetone (2:1) affords the elongated dihydrogen derivative [Os{C6H4C(O)CH3}(eta(2)-H-2)-{eta(1)-(CH3)(2)CO}(PiPr(3))(2)]BF4 (2), which reacts with NaCl and CsF to give Os{C(6)H(4)Q(O)CH3}-X(eta(2) -H-2)((PPr3)-Pr-i)(2) (X = Cl (3), F (4)). The X-ray diffraction studies on 2 and 4 and DFT calculations on the model complexes OsH3{C6H4C(O)CH3}(PH3)(2) (1t), [Os{C6H4C(O)CH3}-(eta(2)-H-2)((HO)-O-2)(PH3)(2)](+) (2t), and Os{C6H4C(O)CH3}X(eta(2)-H-2)(PH3)(2) (X = Cl (3t), F (4t)) suggest that one of the hydrogen atoms bonded to the osmium atom undergoes a cis electrostatic attraction with the L ligand (L = H (1, 1t), (CH3)(2)CO or H2O (2,2t), Cl (3,3t), F (4,4t)), which increases in the sequence (CH3)(2)CO or H2O < Cl :5 F < H. This interaction provokes a lengthening of the hydrogen-hydrogen bond and an increase in the rotation barrier of the elongated dihydrogen ligand. Thus, it is observed that the separation between the hydrogen atoms of the dihydrogen decreases in the sequence It (1.695 Angstrom) > 4t (1.544 Angstrom) > 3t (1.489 Angstrom) > 2t (1.455 Angstrom), whereas the rotation barrier of the dihydrogen increases in the sequence 2 (< 9 kcal.mol(-1)) < 3 (congruent to 9 kcal.mol(-1)) < 4 (10.1 +/- 0.8 kcal.mol(-1)) < 1 (13.9 +/- 0.3 kcal.mol(-1)).

  DOI：

  10.1021/om0342513
• 作为产物：
  描述：

  四氟硼酸-二乙醚络合物 、 OsH3(C6H4C(O)CH3)(P(i)Pr3)2 、 丙酮 以 乙醚 、 丙酮 为溶剂， 以81%的产率得到[Os(C6H4C(O)CH3)(η2-H2)(η1-(CH3)2CO)(P(i)Pr3)2]BF4
  参考文献：
  名称：

  Influence of the Cis Ligand on the H−H Separation and the Rotation Barrier of the Dihydrogen in Osmium-Elongated Dihydrogen Complexes Containing an Ortho-Metalated Ketone

  摘要：

  Treatment of the complex OsH3{C6H4C(O)CH3}((PPr3)-Pr-i)(2) (1) with HBF4.OEt2 in diethyl ether-acetone (2:1) affords the elongated dihydrogen derivative [Os{C6H4C(O)CH3}(eta(2)-H-2)-{eta(1)-(CH3)(2)CO}(PiPr(3))(2)]BF4 (2), which reacts with NaCl and CsF to give Os{C(6)H(4)Q(O)CH3}-X(eta(2) -H-2)((PPr3)-Pr-i)(2) (X = Cl (3), F (4)). The X-ray diffraction studies on 2 and 4 and DFT calculations on the model complexes OsH3{C6H4C(O)CH3}(PH3)(2) (1t), [Os{C6H4C(O)CH3}-(eta(2)-H-2)((HO)-O-2)(PH3)(2)](+) (2t), and Os{C6H4C(O)CH3}X(eta(2)-H-2)(PH3)(2) (X = Cl (3t), F (4t)) suggest that one of the hydrogen atoms bonded to the osmium atom undergoes a cis electrostatic attraction with the L ligand (L = H (1, 1t), (CH3)(2)CO or H2O (2,2t), Cl (3,3t), F (4,4t)), which increases in the sequence (CH3)(2)CO or H2O < Cl :5 F < H. This interaction provokes a lengthening of the hydrogen-hydrogen bond and an increase in the rotation barrier of the elongated dihydrogen ligand. Thus, it is observed that the separation between the hydrogen atoms of the dihydrogen decreases in the sequence It (1.695 Angstrom) > 4t (1.544 Angstrom) > 3t (1.489 Angstrom) > 2t (1.455 Angstrom), whereas the rotation barrier of the dihydrogen increases in the sequence 2 (< 9 kcal.mol(-1)) < 3 (congruent to 9 kcal.mol(-1)) < 4 (10.1 +/- 0.8 kcal.mol(-1)) < 1 (13.9 +/- 0.3 kcal.mol(-1)).

  DOI：

  10.1021/om0342513