[Ir(H)(η2-C6H4P(t-Bu)2)(P(t-Bu)2(Ph))]tetrakis[3,5-bis(trifluoromethyl)phenyl]borate | 219791-58-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [Ir(H)(η2-C6H4P(t-Bu)2)(P(t-Bu)2(Ph))]tetrakis[3,5-bis(trifluoromethyl)phenyl]borate
• 英文别名: ditert-butyl(phenyl)phosphane;ditert-butyl(phenyl)phosphane;iridium(2+) monohydride;tetrakis[3,5-bis(trifluoromethyl)phenyl]boranuide
• CAS: 219791-58-9；215515-76-7
• 化学式: C₂₈H₄₆IrP₂*C₃₂H₁₂BF₂₄
• 分子量: 1500.06
• InChiKey: YCAICOVMVOZVKD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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

• 作为产物：
  描述：

  [Ir(H)(η2-C6H4P(t-Bu)2)(P(t-Bu)2(Ph))2(Cl)] 、 四(3,5-二(三氟甲基)苯基)硼酸钠 以 二氯甲烷 为溶剂， 以71%的产率得到[Ir(H)(η2-C6H4P(t-Bu)2)(P(t-Bu)2(Ph))]tetrakis[3,5-bis(trifluoromethyl)phenyl]borate
  参考文献：
  名称：

  Computational and Experimental Test of Steric Influence on Agostic Interactions:  A Homologous Series for Ir(III)

  摘要：

  Chloride abstraction (using NaBAr'(4), Ar' = 3,5-(CF3)(2)C6H3) from Ir(H)(2)Cl((PBu2Ph)-Bu-t)(2) gives cis,trans-Ir(H)(2)((PBu2Ph)-Bu-t)(2)(+), which has two agostic interactions with methyl C-H groups on different Bu-t groups. The molecule exists as diastereomers, due to stereochemistry at P. Chloride can be similarly abstracted from ortho-metalated IrH(eta(2)-(C6H4PBu2)-Bu-t)Cl((PBu2Ph)-Bu-t) to give square-pyramidal IrH(eta(2)-(C6H4PBu2)-Bu-t)((PBu2Ph)-Bu-t)(+), which has only one agostic interaction, involving a (BuC)-Bu-t-H bond; steric constraints on each phosphine leave no more C-H bonds available to donate to the remaining empty Ir(III) orbital. The smaller ligand PCy2Ph yields only the tris-phosphine complex Ir(H)(2)(PCy2Ph)(3+), and this is shown to have a square-pyramidal structure with one agostic cyclohexyl group and large P-ax-Ir-P angles (104-106 degrees). The analogous Ir(H)(2)((PPr2Ph)-Pr-i)(3)(+) has similar inter-phosphorus angles, but no agostic interaction. Geometrical optimization of IrH2L3+ (PCy2Ph, (PPr2Ph)-Pr-i) with the hybrid quantum mechanics/molecular mechanics (QM/MM) method (IMOMM) at the IMOMM (B3LYP:MM3) and IMOMM (MP2:MM3) levels permits a more detailed understanding of the influence of steric factors on the occurrence of an agostic bond. The MP2/MM3 method gives the results in closer agreement with experiment. Steric factors place the agostic bond in the vicinity of the metal center but at a distance that is too long to be considered as bonding. The electron-donating ability of the C-H bond and the electron accepting capacity of the metal center, which are introduced only at the QM level, bring the two partners in a bonding situation.

  DOI：

  10.1021/ja981727e