[Ir(diphenyl phenylphosphonite-2H)(1,2-bis(diphenylphosphino)benzene)Cl] | 1356834-98-4

• 英文名称: [Ir(diphenyl phenylphosphonite-2H)(1,2-bis(diphenylphosphino)benzene)Cl]
• CAS: 1356834-98-4
• 化学式: C₄₈H₃₇ClIrO₂P₃
• 分子量: 966.415
• InChiKey: NUICLHPYTATYRN-UHFFFAOYSA-M

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：

  [Ir(diphenyl phenylphosphonite-2H)(1,2-bis(diphenylphosphino)benzene)Cl] 、 potassium thioacyanate 以 N,N-二甲基甲酰胺 为溶剂， 以85%的产率得到[Ir(diphenyl phenylphosphonite-2H)(1,2-bis(diphenylphosphino)benzene)(NCS)]
  参考文献：
  名称：

  Stepwise Formation of Iridium(III) Complexes with Monocyclometalating and Dicyclometalating Phosphorus Chelates

  摘要：

  With the motivation of assembling cyclometalated complexes without nitrogen-containing heterocycle, we report here the design and systematic synthesis of a class of Ir(III) metal complexes functionalized with facially coordinated phosphite (or phosphonite) dicyclometalate tripod, together with a variety of phosphine, chelating diphosphine, or even monocyclometalate phosphite ancillaries. Thus, treatment of [IrCl3(tht)(3)] with stoichiometric amount of triphenylphosphite (or diphenyl phenylphosphonite), two equiv of PPh3, and in presence of NaOAc as cyclometalation promoter, gives formation of respective tripodal dicyclometalating complexes [Ir(tpit)(PPh3)(2)Cl] (2a), [Ir(dppit)(PPh3)(2)Cl] (2b), and [Ir(dppit)(PMe2Ph)(2)Cl] (2c) in high yields, where tpitH(2) = triphenylphosphite and dppitH(2) = diphenyl phenylphosphonite. The reaction sequence that afforded these complexes is established. Of particular interest is isolation of an intermediate [Ir(tpitH)(PPh3)(2)Cl-2] (1a) with monocyclometalated phosphite, together with the formation of [Ir(tpit)(tpitH)(PPh3)] (3a) with all tripodal, bidentate, and monodentate phosphorus donors coexisting on the coordination sphere, upon treatment of 2a with a second equiv of triphenylphosphite. Spectroscopic studies were performed to explore the photophysical properties. For all titled Ir(III) complexes, virtually no emission can be observed in either solution at room temperature or 77 K CH2Cl2 matrix. Time-dependent DFT calculation indicates that the lowest energy triplet manifold involves substantial amount of metal centered (MC)-M-3 dd contribution. Due to its repulsive potential energy surface (PES) that touches the PES of ground state, the (MC)-M-3 dd state executes predominant nonradiative deactivation process.

  DOI：

  10.1021/ic202090j
• 作为产物：
  描述：

  [Ir(diphenyl phenylphosphonite-2H)(triphenylphosphine)2Cl] 、 1,2-双(二苯基膦基)苯 以 萘烷 为溶剂， 以95%的产率得到[Ir(diphenyl phenylphosphonite-2H)(1,2-bis(diphenylphosphino)benzene)Cl]
  参考文献：
  名称：

  Stepwise Formation of Iridium(III) Complexes with Monocyclometalating and Dicyclometalating Phosphorus Chelates

  摘要：

  With the motivation of assembling cyclometalated complexes without nitrogen-containing heterocycle, we report here the design and systematic synthesis of a class of Ir(III) metal complexes functionalized with facially coordinated phosphite (or phosphonite) dicyclometalate tripod, together with a variety of phosphine, chelating diphosphine, or even monocyclometalate phosphite ancillaries. Thus, treatment of [IrCl3(tht)(3)] with stoichiometric amount of triphenylphosphite (or diphenyl phenylphosphonite), two equiv of PPh3, and in presence of NaOAc as cyclometalation promoter, gives formation of respective tripodal dicyclometalating complexes [Ir(tpit)(PPh3)(2)Cl] (2a), [Ir(dppit)(PPh3)(2)Cl] (2b), and [Ir(dppit)(PMe2Ph)(2)Cl] (2c) in high yields, where tpitH(2) = triphenylphosphite and dppitH(2) = diphenyl phenylphosphonite. The reaction sequence that afforded these complexes is established. Of particular interest is isolation of an intermediate [Ir(tpitH)(PPh3)(2)Cl-2] (1a) with monocyclometalated phosphite, together with the formation of [Ir(tpit)(tpitH)(PPh3)] (3a) with all tripodal, bidentate, and monodentate phosphorus donors coexisting on the coordination sphere, upon treatment of 2a with a second equiv of triphenylphosphite. Spectroscopic studies were performed to explore the photophysical properties. For all titled Ir(III) complexes, virtually no emission can be observed in either solution at room temperature or 77 K CH2Cl2 matrix. Time-dependent DFT calculation indicates that the lowest energy triplet manifold involves substantial amount of metal centered (MC)-M-3 dd contribution. Due to its repulsive potential energy surface (PES) that touches the PES of ground state, the (MC)-M-3 dd state executes predominant nonradiative deactivation process.

  DOI：

  10.1021/ic202090j