(2-(3,5-difluorophenyl)benzoxazolato-N,C2)2IrIII(μ-Cl)2IrIII(2-(3,5-difluorophenyl)benzoxazolato-N,C2)2 | 1073055-85-2

• 英文名称: (2-(3,5-difluorophenyl)benzoxazolato-N,C2)2IrIII(μ-Cl)2IrIII(2-(3,5-difluorophenyl)benzoxazolato-N,C2)2
• 英文别名: (2-(3,5-difluorophenyl)benzoxazolato-N,C²)₂Ir^III(μ-Cl)₂Ir^III(2-(3,5-difluorophenyl)benzoxazolato-N,C²)₂；(dfpbo)₂Ir^III(μ-Cl)₂Ir^III(dfpbo)₂；(2-(3,5-difluorophenyl)benzoxazolato)2Ir(μ-Cl)2Ir(2-(3,5-difluorophenyl)benzoxazolato)2；[(2-(3,5-difluorophenyl)benzoxazolato-N,C(2'))2Ir(μ-Cl)]2；[(2-(3,5-difluorophenyl)benzoxazolato-N,C(2))Ir(μ-Cl)]2；[(2-(3,5-difluorophenyl)benzoxazolato-N,C2)2Ir(μ-Cl)]2；(fpbo)2Ir(μ-Cl)2Ir(fpbo)2
• CAS: 1073055-85-2
• 化学式: C₅₂H₂₄Cl₂F₈Ir₂N₄O₄
• 分子量: 1376.12
• InChiKey: JKVMYFPMPQZKQV-UHFFFAOYSA-L

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：

  (2-(3,5-difluorophenyl)benzoxazolato-N,C2)2IrIII(μ-Cl)2IrIII(2-(3,5-difluorophenyl)benzoxazolato-N,C2)2 在 K₂CO₃ 作用下， 以 乙二醇乙醚 、 甲苯 为溶剂， 以60%的产率得到[(2-(3,5-difluorophenyl)benzoxazolato-N,C2)2Ir]2(μ-Cl)*(dichloromethane)
  参考文献：
  名称：

  An 18+δ iridium dimer releasing metalloradicals spontaneously

  摘要：

  从二铱（III）核心[(dfpbo)2Ir(δ-Cl)]2（dfpbo = 2-(3.5-二氟苯基)苯并恶唑-N,C2）中还原消除桥接的氯，得到了铱二聚体[(fpbo)2Ir]2(δ-Cl)，该二聚体显示出具有弯曲桥接的 18+δ 结构，在室温下可在溶液中自发释放出金属卤化物。

  DOI：

  10.1039/c0dt00605j
• 作为产物：
  描述：

  [(2-(3,5-difluorophenyl)benzoxazolato-N,C(2))IrCl(P(C6H4OH)3)] 在 air 作用下， 以 水 、 甲苯 为溶剂， 生成 (2-(3,5-difluorophenyl)benzoxazolato-N,C2)2IrIII(μ-Cl)2IrIII(2-(3,5-difluorophenyl)benzoxazolato-N,C2)2
  参考文献：
  名称：

  Water Attack Umpolung Aromatic Systems To Release Hydrogen

  摘要：

  The synthesis and structures of a series of cyclometalated iridium(III) complexes based on benzoxazole derivatives and triphenylphospine are reported. These complexes have a general formula (C boolean AND N)(2)Ir(Cl)(pph(3)) [where C boolean AND N is a monoanionic cyclometalating ligand, dfpbo = (difluorophenyl)benzoxazolato, pbo = 2-phenylbenzoxazolato, nbo = 2-(2-naphthyl)benzoxazolato, and pph(3) is a triphenylphospine ligand]. The complexes (dfpbo)(2)Ir(Cl)(pph(3)) (2a), (pbo)(2)Ir(Cl)(pph(3)) (2b), and (nbo)(2)Ir (Cl)(pph(3)) (2c) have been structurally characterized by X-ray crystallography. Complex 2a shows facile umpolung in the phenyl rings of the arylphosphine ligand and displays a catalytic propensity for water splitting.

  DOI：

  10.1021/ic1025944

文献信息

• Diiridium Bimetallic Complexes Function as a Redox Switch To Directly Split Carbonate into Carbon Monoxide and Oxygen
  作者：Tsun-Ren Chen、Fang-Siou Wu、Hsiu-Pen Lee、Kelvin H.-C. Chen

  DOI：10.1021/jacs.6b00715

  日期：2016.3.23

  bimetallic complexes exhibit a special type of oxidation-reduction reaction that could directly split carbonate into carbon monoxide and molecular oxygen via a low-energy pathway needing no sacrificial reagent. One of the bimetallic complexes, Ir(III)(μ-Cl)2Ir(III), can catch carbonato group from carbonate and reduce it to CO. The second complex, the rare bimetallic complex Ir(IV)(μ-oxo)2Ir(IV), can react

  一对二铱双金属配合物表现出一种特殊类型的氧化还原反应，可以通过不需要牺牲试剂的低能量途径直接将碳酸盐分解为一氧化碳和分子氧。其中一种双金属配合物 Ir(III)(μ-Cl)2Ir(III) 可以从碳酸盐中捕获碳酸根并将其还原为 CO。第二种配合物，稀有的双金属配合物 Ir(IV)(μ-oxo)2Ir (IV)、与氯反应，通过铱离子和氯原子的协同氧化作用，通过氧离子的氧化作用放出O2。关键反应所需的活化能非常低（~20 kJ/mol），远低于 CO2 中 C=O 键的解离能（~750 kJ/mol）。
• Cyclometalated Iridium(III) Complexes with Ligand Effects on the Catalytic C–H Bond Activation of Toluene
  作者：Tsun‐Ren Chen、Pei‐Chun Liu、Hsiu‐Pen Lee、Fang‐Siou Wu、Kelvin H. ‐C. Chen

  DOI：10.1002/ejic.201601548

  日期：2017.4.3

  New cyclometalated iridium (III) complexes are designed, prepared and applied to a catalytic system for carbon-hydrogen bond activation (CHA) of toluene using a clean, highly efficient and environmentally friendly process. These complexes have the general formula (C^N)2Ir(N^O). The C^N ligands are monoanionic bidentate cyclometalating ligands, including 2-phenylpyridinato (ppy), 2-phenylbenzoxazolato

  新的环金属化铱 (III) 配合物被设计、制备并应用于使用清洁、高效和环保工艺的甲苯碳氢键活化 (CHA) 催化系统。这些配合物具有通式 (C^N)2Ir(N^O)。C^N配体是单阴离子双齿环金属化配体，分别包括2-苯基吡啶根(ppy)、2-苯基苯并恶唑根(pbo)和2-(3.5-二氟苯基)苯并恶唑根(dfpbo)；(N^O)配体也是单阴离子双齿环金属化配体吡啶甲酸甲酯(pic)。配合物 (ppy)2Ir(pic) (1)、(pbo)2Ir(pic) (2) 和 (dfpbo)2Ir(pic) (3) 通过 1H NMR、13C NMR、FAB-MS 和 X 射线进行结构表征晶体学。当使用配合物 1-3 作为催化剂时，甲苯催化 CHA 氧化所需的活化能非常低，在 14 之间。4 和 25.5 kcal mol-1。催化频率（TOF）相当高（高达 4.0×103 Mol甲苯 Molcatalyst-1
• A Novel Cyclometalated Dimeric Iridium Complex, [(dfpbo)₂Ir]₂ [dfpbo = 2-(3,5-Difluorophenyl)benzoxazolato-<i>N</i>,<i>C</i>^2′], Containing an Unsupported Ir^II−Ir^II Bond
  作者：Hsiu-Pen Lee、Yi-Fen Hsu、Tsun-Ren Chen、Jhy-Der Chen、Kelvin H.-C. Chen、Ju-Chun Wang

  DOI：10.1021/ic8019952

  日期：2009.2.16

  An unusual iridium complex, [(dfpbo)2Ir]2 [dfpbo = 2-(3,5-difluorophenyl)benzoxazolato-N,C2′], which is the first dimeric iridium complex composed of two bis-cyclometalated IrII structures connected by an unsupported IrII−IrII bond, has been synthesized and fully characterized. Under mild conditions of neutral pH at room temperature, this complex dissociated spontaneously to form the stable radical

  一种不寻常的铱络合物，[（dfpbo）2 Ir] 2 [dfpbo = 2-（3,5-二氟苯基）苯并恶唑-N，C 2' ]，它是由两个双环金属化的Ir II结构组成的第一个二聚铱络合物通过不支持的Ir II -Ir II键连接的分子已被合成并充分表征。在室温下中性pH的温和条件下，该络合物自发解离形成稳定的自由基[Ir（dfpbo）2 ] •。
• Ligand effect of cyclometallated iridium(<scp>iii</scp>) complexes on <i>N</i>-alkylation of amines in hydrogen borrowing reactions
  作者：Yi-Sheng Chen、Siang-Yu Chiu、Chia-Ying Li、Tsun-Ren Chen、Jhy-Der Chen

  DOI：10.1039/d3ra07184g

  日期：——

  general formula (C^N)2Ir(μ-Cl)2Ir(C^N)2 (C^N = bidentate ligand with carbon and nitrogen donor atoms) were prepared and used in catalytic systems for N-alkylation of amines through the hydrogen borrowing pathway. Triphenylphosphine derivatives were used as auxiliary in catalytic systems to provide excellent conversion of amines to N-alkylation products in yields ranging from 57% to 100%. The catalytic ability

  制备了通式为 (C^N)2Ir(μ-Cl)2Ir(C^N)2（C^N = 具有碳和氮供体原子的二齿配体）的双核铱配合物，并将其用于 N-烷基化催化体系通过借氢途径合成胺。三苯基膦衍生物在催化系统中用作助剂，可将胺出色地转化为 N-烷基化产物，收率范围为 57% 至 100%。催化剂的催化能力取决于其配位配体的结构，包括双齿配体(C^N)和三苯基膦衍生物。这些催化系统通过氢自转移策略采用环境友好且可持续的反应过程，使用容易获得的醇作为烷基化剂，而不需要碱、溶剂和其他添加剂，在合成和制药工业中显示出潜力。
• Synthesis and characterization of cyclometalated iridium(III) complexes containing benzoxazole derivatives and different ancillary ligands
  作者：Tsun-Ren Chen

  DOI：10.1016/j.jorganchem.2008.06.034

  日期：2008.9

  The synthesis, structures, electrochemistry, and photophysics of a series of cyclometalated iridium(III) complexes based on benzoxazole derivatives and different beta-diketonate ligands are reported. These complexes have a general formula C boolean AND N2Ir(LL') [ where C boolean AND N is a monoanionic cyclometalating ligand; 2-phenylbenzoxazolato (pbo), 2-(4-chlorophenyl) benzoxazolato (cpbo), 2-phenyl-5-chlorobenzoxazolato (pcbo), 2-(3,5-difluorophenyl)benzoxazole (fpbo), or 2-(2-naphthyl)benzoxazolato (nbo), and LL' is an ancillary ligand; acetylacetonate (acac), dibenzoylmethanate (dbm), or 1,1,1,5,5,5-hexafluoroacetylacetonate (hfacac)]. The complexes (pcbo)(2)Ir(acac) (3), (dfpbo)(2)Ir(acac) (4), (cpbo)(2)Ir(dbm) (7), (dfpbo)(2)Ir(dbm) (8), and (dfpbo)(2)Ir(hfacac) (9) have been structurally characterized by X-ray crystallography. All of the complexes show reversible oxidation between 0.45 and 1.07 V, versus Fc/Fc(+), and have short luminescence lifetime (tau = 0.1-1.3 mu s) at room temperature. Except complex 9, the radiative decay rate (k(r)) and nonradiative decay rate (k(nr)) of the (C boolean AND N)(2)Ir(LL') complexes have been determined by using the lifetime and quantum efficiency. The kr ranges between 2.0 x 10(3) and 3.0 x 10(5) s(1) and knr spans a narrower range of values (5.0 x 10(5) to 7.0 x 10(6) s(1)). (C) 2008 Elsevier B.V. All rights reserved.