[Re3(μ-H)2(μ-pyridazine-κN(1):κN(2))(CO)10][Et4N] | 681146-46-3

• 英文名称: [Re3(μ-H)2(μ-pyridazine-κN(1):κN(2))(CO)10][Et4N]
• 英文别名: [N(C2H5)4][Re(CO)10(μ-H)2(μ-η2-pyridazine)]
• CAS: 681146-46-3
• 化学式: C₈H₂₀N*C₁₄H₆N₂O₁₀Re₃
• 分子量: 1051.08
• InChiKey: QUOFVUNFZOHWBS-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：

  [Re3(μ-H)2(μ-pyridazine-κN(1):κN(2))(CO)10][Et4N] 以 甲苯 为溶剂， 生成 [Re(CO)10(μ-H)3(μ-η2-pyridazine)]
  参考文献：
  名称：

  Competition studies on the activation of the C_H bond of diazines by the unsaturated triangular cluster anion [Re3(μ-H)4(CO)10]−

  摘要：

  The reactions of the unsaturated cluster anion [Re-3(mu-H)(4)(CO)(10)](-) (1) with 1,2-, 1,3- and 1,4-diazines (used as solvents) have been investigated. The reaction with 1,2-diazine at room temperature gives quantitatively the anion [Re-3(mu-H)(2)(mu-eta(2)-N2C4H4)(CO)(10)](-) (3), containing a diazine bridging through the two N atoms, characterised by single crystal X-ray analysis. The orthometallated isomer [Re-3(mu-H)(3)(mu-eta(2)-N2C4H3)(CO)(10)](-) (4) was obtained by refluxing 3 in toluene. The reaction of [NEt4]1 in molten 1,4-diazine (60degreesC) affords the anion [Re-3(mu-H)(3)(mu-eta(2)-N2C4H3)(CO)(10)](-) (5), containing orthometallated pyrazine. The slow reaction of [NEt4]1 with 1,3-diazine at room temperature gives two orthometallated isomers 6, corresponding to the metallation of carbon C2 (6a) and C6 (6b), respectively (6b/6a ratio ca. 1.2). Differently from what previously found for the analogous cluster anion containing orthometallated pyridine, the metallation reaction of diazines showed little reversibitity, and poor conversion of 5 and 6 to the starting anion 1 was observed after several days under 100 atm of H-2). Competition experiments, performed by dissolving [NEt4]1 in equimolar mixtures of pyridine/pyrazine or pyridine/pyrimidine, showed that the anion with metallated pyridine was the kinetically preferred product and that at longer times it slowly converted to the derivatives with metallated diazines (5 or 6). (C) 2003 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s1381-1169(03)00318-2
• 作为产物：
  描述：

  哒嗪 、 [NEt4N][Re3(μ-H)4(CO)10] 以 neat (no solvent) 为溶剂， 以52.8%的产率得到[Re3(μ-H)2(μ-pyridazine-κN(1):κN(2))(CO)10][Et4N]
  参考文献：
  名称：

  Competition studies on the activation of the C_H bond of diazines by the unsaturated triangular cluster anion [Re3(μ-H)4(CO)10]−

  摘要：

  The reactions of the unsaturated cluster anion [Re-3(mu-H)(4)(CO)(10)](-) (1) with 1,2-, 1,3- and 1,4-diazines (used as solvents) have been investigated. The reaction with 1,2-diazine at room temperature gives quantitatively the anion [Re-3(mu-H)(2)(mu-eta(2)-N2C4H4)(CO)(10)](-) (3), containing a diazine bridging through the two N atoms, characterised by single crystal X-ray analysis. The orthometallated isomer [Re-3(mu-H)(3)(mu-eta(2)-N2C4H3)(CO)(10)](-) (4) was obtained by refluxing 3 in toluene. The reaction of [NEt4]1 in molten 1,4-diazine (60degreesC) affords the anion [Re-3(mu-H)(3)(mu-eta(2)-N2C4H3)(CO)(10)](-) (5), containing orthometallated pyrazine. The slow reaction of [NEt4]1 with 1,3-diazine at room temperature gives two orthometallated isomers 6, corresponding to the metallation of carbon C2 (6a) and C6 (6b), respectively (6b/6a ratio ca. 1.2). Differently from what previously found for the analogous cluster anion containing orthometallated pyridine, the metallation reaction of diazines showed little reversibitity, and poor conversion of 5 and 6 to the starting anion 1 was observed after several days under 100 atm of H-2). Competition experiments, performed by dissolving [NEt4]1 in equimolar mixtures of pyridine/pyrazine or pyridine/pyrimidine, showed that the anion with metallated pyridine was the kinetically preferred product and that at longer times it slowly converted to the derivatives with metallated diazines (5 or 6). (C) 2003 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s1381-1169(03)00318-2

文献信息

• Dynamic processes in hydrido-carbonyl trirhenium clusters containing bridging nitrogen heterocyclic ligands: An NMR investigation
  作者：Daniela Maggioni、Monica Panigati、Tiziana Beringhelli、Giuseppe D’Alfonso

  DOI：10.1016/j.jorganchem.2011.08.044

  日期：2011.11

  recognized, and its activation parameters, in C2D2Cl4, have been determined (Ea = 68(3) kJ mol−1). The exchange has been attributed to the rotation of the apical H2Re(CO)4 fragment with respect to the Re2(μ-pz) basal fragment, a process analogous to that previously observed in the unsaturated dianion [Re3(μ-H)3(CO)10] 2− (2) and in the monoanion [Re3(μ-H)3(μ–NC5H4–κN1:κC6)(CO)10]− (1), containing a bridging

  在三角簇发生的动态过程[回复3（μ-H）3（μ-PZ- κN 1：κN 2）（CO）10 ] -（PZ =吡，4），[重3（μ-H）2（μ-pydz- κN 1：κN 2）（CO）10 ] -（pydz =哒嗪，5）和[回复3（μ-H）3（μ-pydz- κN 1：κN 2）（CO）10 ]（6），已由1 H和13 C NMR。在吡唑特衍生物4的交换（ķ  ≈1秒-1在320 K）之间在两个羰基的反式-diaxial心尖的位置已经被识别，它的激活参数，在C 2 d 2氯4，已被确定（E a  ＝ 68（3）kJ mol -1）。交换归因于顶端H 2 Re（CO）4片段相对于Re 2（μ-PZ）基础片段的旋转，该过程类似于先前在不饱和二价阴离子[Re 3（μ-H）3（CO）10 ] 2-（2）和一价阴离子[回复3（μ-H）3（μ - NC 5 H ^ 4 - κN 1：κC 6）（CO）10