| 104453-06-7

• CAS: 104453-06-7
• 化学式: C₄₁H₄₀Cl₂IrP₃
• 分子量: 888.816
• InChiKey: MJTOKHJAROPYFJ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  9.5
• 重原子数：
  47.0
• 可旋转键数：
  6.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  在 Cl₂ 作用下， 以 二氯甲烷 为溶剂， 生成 IrCl3(tripod)
  参考文献：
  名称：

  一些铱（I）和铱（III）与三脚架状配体CH 3 C（CH 2 PPh 2）3（triphos）和[IrCl（CO）（triphos）]的X射线晶体结构络合

  摘要：

  化合物[IrCl（CO）（triphos）]（1）已被重新研究，并报道了其X射线晶体结构。该晶体是斜方晶系，空间群PBCA，具有一个18.941（6），b 22.193（8），Ç 17.501（7），Ž = 8的结构经重原子方法来解决和由精制全矩阵最不对6462次反射的常规R因子值0.074平方。金属原子的配位是三角双锥体，三个磷原子占据一个轴向和两个赤道位置。当Cl轴向协调时，另一赤道位置被CO占据。

  DOI：

  10.1016/0022-328x(85)80351-x
• 作为产物：
  描述：

  IrCl3(tripod) 在 H₂ 作用下， 以 甲醇 为溶剂， 以90%的产率得到
  参考文献：
  名称：

  一些铱（I）和铱（III）与三脚架状配体CH 3 C（CH 2 PPh 2）3（triphos）和[IrCl（CO）（triphos）]的X射线晶体结构络合

  摘要：

  化合物[IrCl（CO）（triphos）]（1）已被重新研究，并报道了其X射线晶体结构。该晶体是斜方晶系，空间群PBCA，具有一个18.941（6），b 22.193（8），Ç 17.501（7），Ž = 8的结构经重原子方法来解决和由精制全矩阵最不对6462次反射的常规R因子值0.074平方。金属原子的配位是三角双锥体，三个磷原子占据一个轴向和两个赤道位置。当Cl轴向协调时，另一赤道位置被CO占据。

  DOI：

  10.1016/0022-328x(85)80351-x

文献信息

• Triphos Iridium(III) Halide Complex Photochemistry: Triphos Arm Dissociation
  作者：Andreas Ross、Paul R. Sharp

  DOI：10.1021/ic401835d

  日期：2013.11.4

  1-tris(diphenylphosphinomethyl)ethane; X = Cl, Br) yields an insoluble product believed to be oligomeric [Ir(triphos)X3]n with bridging triphos and halide ligands. Refluxing pyridine (py) dissolves the insoluble photoproducts ultimately yielding the dangling triphos complexes mer-Ir(κ2-triphos)(py)X3. Oxidation of the P center of the dangling arm of Ir(κ2-triphos)(py)Cl3 yields mer-Ir(κ2-P,P-triphosO)(py)Cl3 (triphosO

  Ir（triphos）X 3（triphos = 1,1,1-tris（diphenylphosphinomethyl）ethane; X = Cl，Br）的光解产生不溶性产物，该产物被认为是低聚的[Ir（triphos）X 3 ] n，具有三桥联和卤化物配体。回流吡啶（PY）溶解不溶性光化最终产生的悬空三膦络合物聚体-Ir（κ 2 -triphos）（PY）X 3。IR的悬挂臂（κ的P-中心的氧化2 -triphos）（PY）氯3吨的产量聚体-Ir（κ 2 -P，P-triphosO）（PY）氯3（triphosO =的MeC（CH 2 P（ O）Ph 2）（CH 2PPh 2）2），其通过单晶X射线衍射表征。聚体-Ir（κ 2 -triphos）（PY）氯3时的Ir（三膦）氯也形成3在吡啶（φ= 26％）的存在下光解。两个聚体-Ir（κ 2 -triphos）（PY）氯3和聚体-Ir（κ
• HDS Model Systems. Coordination, Opening, and Hydrogenation of Benzo[b]thiophene at Iridium
  作者：Claudio Bianchini、Andrea Meli、Maurizio Peruzzini、Francesco Vizza、Simonetta Moneti、Veronica Herrera、Roberto A. Sanchez-Delgado

  DOI：10.1021/ja00089a027

  日期：1994.5

  The eta 4-benzene complexes [(triphos)Ir(C6H6)]Y (Y = BPh(4), 1a; PF6, 1b) react with benzo[b]thiophene (BT) at room temperature to give the unprecedented [(triphos)Ir(eta(3)-C,C,S-C8H6S)]Y (Y = BPh(4), 2a; PF6, 2b) in which intact BT is coordinated to the metal center through the S atom and the C-2=C-3 bond. 2a and 2b are transformed upon mild thermolysis into the iridabenzothiabenzene complexes [(triphos)Ir(eta(2)-C,S-C8H6S)]Y (Y = BPh(4), 3a; PF6, 3b). An X-ray analysis has been carried out on 3a.1.5THF.0.5EtOH. The coordination geometry around iridium may be described as a distorted trigonal-bipyramid, the metal center being surrounded by the three phosphorus atoms of triphos and by a carbon and a sulfur atom from a CS-cleaved BT molecule. Crystal data: triclinic, space group P (1) over bar, a 17.391(3) Angstrom, b = 16.957(4) Angstrom, c = 12.795(3) Angstrom, alpha = 77.51(2)degrees, beta = 80.98(2)degrees, gamma = 75.50(2)degrees, Z = 2, d(calcd) = 1.31 g cm(-3), n(obsd) = 7636, R = 0.072. Interaction of 2a with CO (1 atm, 20 degrees C) yields [(triphos)Ir(CO)(2)]BPh(4) (4) plus free BT, whereas 3a requires more drastic conditions (5 atm, 70 degrees C) to eliminate BT and produce 4. 2a also reacts with H-2 (1 atm, 20 degrees C) to produce [(triphos)Ir(H)(2)(eta(1)-S-BT)]BPh(4) (5), which can be independently prepared by treatment of [(triphos)Ir(H)(2)(THF)]BPh(4) with BT; at 5 atm H-2, free BT is obtained together with [(triphos)Ir(H)(3)], BPh(3), and benzene, as a result of a heterolytic splitting of H-2 at the [(triphos)Ir(H)(2)](+) fragment assisted by the BPh(4)(-), counteranion. The C-S-cleaved BT in 3a is readily hydrogenated (5 atm, 20 degrees C) to 2-ethylbenzenethiolate, producing [(triphos)Ir(H)(2)o-S-(C6H4)C2H5}] (8) plus BPh(3) and benzene also via heterolytic splitting of H-2 assisted by BPh(4)(-), protonolysis of 8 with 2 equiv HCl produces (triphos)IrCl3 with concomitant liberation of 2-ethylbenzenethiol, a primary product of BT HDS. If the PF6- analogue 3b is used instead, the reaction with H-2 under identical conditions yields the thiolate-bridged dimer [(triphos)IrHmu-o-S(C6H4)C2H5}2HIr(triphos)](PF6)(2) (9b). 3a also reacts with LiHBEt(3) to give [(triphos)Ir(H)(eta(2)-C,S-C8H6S)] (11), which converts in THF solution at 66 degrees C into [(triphos)Ir(eta(3)-S(C6H4)CH=CH2)] (12) by hydride migration to C-2; neither 11 nor 12 react with H-2 under mild conditions. Addition of HBF4.OEt(2) to 12 yields [(triphos)Ir(eta(4)-S(C6H4)C(H)Me)]BF4 (13c), which does react with H-2 even at 1 atm to give the thiolate-bridged dimer [(triphos)IrHmu-o-S(C6H4)C2H5}2HIr(triphos)](BF4)(2) (9c). 13c also reacts with H- to give [(triphos)IrH(eta(2)-S(C6H4)C(H)Me)] (14), which in turn reacts with H-2 and HBF4.OEt(2) to yield 8 and 9c, respectively.
• Hydrodesulfurization model systems. Homogeneous and heterogeneous (solid-gas) hydrogenation of benzothiophene at iridium
  作者：Claudio Bianchini、Andrea Meli、Maurizio Peruzzini、Francesco Vizza、Piero Frediani、Veronica Herrera、Roberto A. Sanchez-Delgado

  DOI：10.1021/ja00069a061

  日期：1993.8