(dippe)Ir(Bpin)3 | 1196109-24-6

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: (dippe)Ir(Bpin)3
• 英文别名: (1,2-bis(diisopropylphosphino)ethane)Ir(B-pinacolate)3
• CAS: 1196109-24-6
• 化学式: C₃₂H₆₈B₃IrO₆P₂
• 分子量: 835.489
• InChiKey: CUODXLOPFAQCCS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.96
• 重原子数：
  44.0
• 可旋转键数：
  7.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  55.38
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  胡椒环 、 (dippe)Ir(Bpin)3 以 环己烷 为溶剂， 反应 0.25h， 生成 2-(benzo[d][1,3]dioxol-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
  参考文献：
  名称：

  Electronic effects in iridium C–H borylations: insights from unencumbered substrates and variation of boryl ligand substituents

  摘要：

  实验和理论支持 C–H 硼化模型，其中过渡态存在显着的质子转移特征。

  DOI：

  10.1039/c0cc02041a
• 作为产物：
  描述：

  以 氘代苯 为溶剂， 生成 (dippe)Ir(Bpin)3 、 频那醇硼烷
  参考文献：
  名称：

  Reversible Borylene Formation from Ring Opening of Pinacolborane and Other Intermediates Generated from Five-Coordinate Tris-Boryl Complexes: Implications for Catalytic C–H Borylation

  摘要：

  Catalytic C-H borylation using the five-coordinate tris-boryl complex (dippe)Ir(Bpin)(3) (5a, dippe = 1,2-bis(diisopropylphosphino) ethane) has been examined using P-31 {H-1} and NMR spectroscopy. Compound 5a was shown to react rapidly and reversibly with HBpin to generate a six-coordinate borylene complex, (dippe)Ir(H)-(Bpin)(2)(BOCMe(2)CMe(2)OBpin) (6), whose structure was confirmed by X-ray crystallography. Under catalytic conditions, the H-2 generated from C-H borylation converted compound 6 to a series of intermediates. The first is tentatively assigned from P-31{H-1} and H-1 NMR spectra as (dippe)Ir(H(2)B(3)pin(3)) (7), which is the product of formal H-2 addition to compound 5a. As catalysis progressed, compound 7 was converted to a new species with the formula (dippe)Ir(H(3)B(2)pin(2)) (8), which arose from H-2 addition to compound 7 with loss of HBpin. Compound 8 was characterized by P-31{H-1} and H-1 NMR spectroscopy, and its structure was confirmed by X-ray crystallography, where two molecules with different ligand orientations were found in the unit cell. DFT calculations support the formulation of compound 8 as an Ir-III agostic borane complex, (dippe)IrH2(Bpin)(eta(2)-HBpin). Compound 8 was gradually converted to (dippe)Ir(H(4)Bpin) (9), which was characterized by P-31{H-1} and H-1 NMR spectroscopy and X-ray crystallography. DFT calculations favor its formulation as an agostic borane complex of Ir-III with the formula (dippe)IrH3(eta(2)-HBpin). Compound 9 reacted further with H-2 to afford the dimeric structure [(dippe)IrH2(mu(2)-H)](2) (10), which was characterized by H-1 NMR and X-ray crystallography. Compounds 7-10 are in equilibrium when H2 and HBpin are present.

  DOI：

  10.1021/acs.organomet.5b00525
• 作为试剂：
  描述：

  2-甲基噻吩 、 频那醇硼烷 在 (dippe)Ir(Bpin)3 作用下， 以 全氘代环己烷 为溶剂， 反应 4.0h， 生成 5-甲基噻吩-2-硼酸频那醇酯
  参考文献：
  名称：

  Reversible Borylene Formation from Ring Opening of Pinacolborane and Other Intermediates Generated from Five-Coordinate Tris-Boryl Complexes: Implications for Catalytic C–H Borylation

  摘要：

  Catalytic C-H borylation using the five-coordinate tris-boryl complex (dippe)Ir(Bpin)(3) (5a, dippe = 1,2-bis(diisopropylphosphino) ethane) has been examined using P-31 {H-1} and NMR spectroscopy. Compound 5a was shown to react rapidly and reversibly with HBpin to generate a six-coordinate borylene complex, (dippe)Ir(H)-(Bpin)(2)(BOCMe(2)CMe(2)OBpin) (6), whose structure was confirmed by X-ray crystallography. Under catalytic conditions, the H-2 generated from C-H borylation converted compound 6 to a series of intermediates. The first is tentatively assigned from P-31{H-1} and H-1 NMR spectra as (dippe)Ir(H(2)B(3)pin(3)) (7), which is the product of formal H-2 addition to compound 5a. As catalysis progressed, compound 7 was converted to a new species with the formula (dippe)Ir(H(3)B(2)pin(2)) (8), which arose from H-2 addition to compound 7 with loss of HBpin. Compound 8 was characterized by P-31{H-1} and H-1 NMR spectroscopy, and its structure was confirmed by X-ray crystallography, where two molecules with different ligand orientations were found in the unit cell. DFT calculations support the formulation of compound 8 as an Ir-III agostic borane complex, (dippe)IrH2(Bpin)(eta(2)-HBpin). Compound 8 was gradually converted to (dippe)Ir(H(4)Bpin) (9), which was characterized by P-31{H-1} and H-1 NMR spectroscopy and X-ray crystallography. DFT calculations favor its formulation as an agostic borane complex of Ir-III with the formula (dippe)IrH3(eta(2)-HBpin). Compound 9 reacted further with H-2 to afford the dimeric structure [(dippe)IrH2(mu(2)-H)](2) (10), which was characterized by H-1 NMR and X-ray crystallography. Compounds 7-10 are in equilibrium when H2 and HBpin are present.

  DOI：

  10.1021/acs.organomet.5b00525

文献信息

• Getting the sterics just right: a five-coordinate iridium trisboryl complex that reacts with C–H bonds at room temperature
  作者：Ghayoor A. Chotana、Britt A. Vanchura, II、Man Kin Tse、Richard J. Staples、Robert E. Maleczka, Jr、Milton R. Smith, III

  DOI：10.1039/b914736e

  日期：——

  Five-coordinate boryl complexes relevant to Ir mediated C–H borylations have been synthesized, providing a glimpse of the most fundamental step in the catalytic cycle for the first time.

  与铱介导的C–H borilation相关的五配位硼基配合物已被合成，首次提供了催化循环中最基本步骤的一个概 glimpse。