[IrH(CO)Cl(PPh3)3]BF4 | 79355-74-1

• 英文名称: [IrH(CO)Cl(PPh3)3]BF4
• 英文别名: [IrH(CO)Cl(PPh₃)₃]BF₄；[IrHCl(CO)(triphenylphosphine)3]BF4
• CAS: 79355-74-1
• 化学式: BF₄*C₅₅H₄₆ClIrOP₃
• 分子量: 1130.37
• InChiKey: UEDGELAIXAIDPU-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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

• 作为反应物：
  描述：

  1-戊烯-4-炔-3-醇 、 [IrH(CO)Cl(PPh3)3]BF4 以 四氢呋喃 为溶剂， 以56%的产率得到[IrCl(CO)(triphenylphosphine)2(CH2CHCHC(PPh3)CH)]BF4
  参考文献：
  名称：

  C−H Bond Activation and Subsequent C(sp²)−C(sp³) Bond Formation: Coupling of Bromomethyl and Triphenylphosphine in an Iridium Complex

  摘要：

  Treatment of HC CCH(OH)CH=CH2, with [IrHCl(CO)(PPh3)(3)]BF4 at room temperature afforded an iridacyclohexadiene, [Ir(CH=C(PPh3)CH=CHCH2)Cl(CO)(PPh3)(2)]BF4 (1). The reactivity of complex 1 had been investigated. Reaction of 1 with 1 equiv of bromine produced an iridacyclopentadiene, [Ir(CH=C(PPh3)CH=C(CH2BR))Cl(CO)(PPh3)(2)]BF4 (2). When excess bromine was used, iridacyclopentadiene 2 underwent subsequent intramolecular C(sp(2))-C(sp(3)) coupling between the exocyclic-CH2Br group and a phenyl of the PPh3 ligand, leading to the formation of a fused iridacycle complex, [Ir(CH=C(PPh3)C(Br)=C(CHBr))(P(C6H4)Ph-2)Cl(CO)PPh3]Br-3 (3). A mechanism for the formation of complex 3 starting; from 1 was proposed, in which the process involved a triple C-H activation as well as a rare C(sp(2))-C(sp(3)) reductive elimination.

  DOI：

  10.1021/om100187t

文献信息

• Color-Tuning Strategy for Iridapolycycles [(N^∧N)Ir(C^∧C)ClPPh₃]⁺ by the Synergistic Modifications on Both the C^∧C and N^∧N Units
  作者：Zi-Ao Huang、Qing Lan、Yuhui Hua、Zhixin Chen、Hong Zhang、Zhenyang Lin、Haiping Xia

  DOI：10.1021/acs.organomet.7b00699

  日期：2017.12.26

  reported yet. Herein, a convenient color-tuning strategy for C∧C-based Iridacycles is accomplished with the aid of DFT calculations. The developed synthetic protocol allowed facile modifications on C∧C units and N∧N units via a one-pot synthesis starting from iridium vinyl complexes, accessing the novel phosphorescent iridapolycycles [(N∧N)Ir(C∧C)ClPPh3]+.

  近年来，环金属化的Ir（III）配合物的发光研究吸引了相当大的兴趣。为了满足各个领域中发射波长的需求，铱（III）配合物的策略性发射颜色调节对于它们作为磷光材料的应用至关重要。然而，对于具有稠合的碳环iridacycles一个可行颜色调整方法（C ∧ C）还没有被报道。在此，对于C方便的颜色调整战略∧基于C-Iridacycles与DFT计算的帮助下完成的。发达合成协议允许基于C容易修改∧ C单位和N ∧ N个单位通过一锅合成从铱络合物乙烯开始，接入新型磷光iridapolycycles [（N∧ N）的Ir（C ∧ C）ClPPh 3 ] +。
• Sequential Construction Strategy for Rational Design of Luminescent Iridacycles
  作者：Hui Xu、Zi-Ao Huang、Xugeng Guo、Yuhui Yang、Yuhui Hua、Zexing Cao、Shunhua Li、Haiping Xia

  DOI：10.1021/acs.organomet.5b00652

  日期：2015.9.14

  A convenient and general strategy has been developed to synthesize stable iridapolycydes 5-8. Reaction of arylacetylenes with iridium-hydride complex [IrH(CO)C1(PPh3)(3)]-BF4 via nudeophilic addition, oxidative decarbonylation, and C-H bond activation results in the formation of a series of iridacydopentadiene derivatives, including benzo-iridacydopentadiene 5, naphtho-iridacydopentadiene 6, pyreno-iridacydopentadiene 7, and thieno-iridacydopentadiene 8. These iridapolycydes display high thermal and air stability yet can be further functionalized via facile ligand substitution reactions. As an example, complex 5 was used as a metallosynthon to react with 2,2'-dipyridyl to give intensely luminescent Ir(III) complex 9 bearing one CAC and one NAN ligands. Density functional theory (DFT) calculations reveal that the lowest unoccupied molecular orbitals (LUMOs) of iridapolycydes 5-8 are located on the phosphonium groups while the highest occupied molecular orbitals (HOMOs) are mainly located on the metal-embedded CAC frameworks. Our method offers a sequential construction strategy for constructing luminescent iridacydes, which potentially allows facile tuning of the photoluminescence properties by modulating the CAC and NAN moieties independently.