oxotrimesityliridium(V) | 152386-96-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: oxotrimesityliridium(V)
• 英文别名: oxotrimesityliridium；(2,4,6-trimethylphenyl)3Ir=O；(mes)3Ir=O；Ir(Mes)3=O
• CAS: 152386-96-4
• 化学式: C₂₇H₃₃IrO
• 分子量: 565.778
• InChiKey: ZQXYRLZEGQEFRU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.24
• 重原子数：
  29.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  oxotrimesityliridium(V) 在 sodium dithionite 作用下， 以 乙醚 、 水 为溶剂， 生成 trimesityliridium(III)
  参考文献：
  名称：

  Synthesis and X-ray crystal structure of oxotrimesityliridium(V)

  摘要：

  The interaction of trimesityliridium(III) with trimethylamine oxide gives quantitative yields of the green iridium(V) complex Ir(O)(mes)3, whose X-ray crystal structure has been determined. The oxo compound is also obtained by interaction of dioxygen with Ir(mes)3 and Ir(mes)4. A similar oxo species has also been obtained from Ir(2,6-Me2C6H3)4. The molecular structure of Ir(O)(mes)3 is distorted tetrahedral with Ir=O and Ir-C bond lengths of 1.725(9) and 1.989-2.034(13) angstrom, respectively.

  DOI：

  10.1016/s0277-5387(00)81474-6
• 作为产物：
  描述：

  trimesityliridium(III) 在 O₂ 作用下， 以 氘代苯 为溶剂， 生成 oxotrimesityliridium(V)
  参考文献：
  名称：

  Synthesis and X-ray crystal structure of oxotrimesityliridium(V)

  摘要：

  The interaction of trimesityliridium(III) with trimethylamine oxide gives quantitative yields of the green iridium(V) complex Ir(O)(mes)3, whose X-ray crystal structure has been determined. The oxo compound is also obtained by interaction of dioxygen with Ir(mes)3 and Ir(mes)4. A similar oxo species has also been obtained from Ir(2,6-Me2C6H3)4. The molecular structure of Ir(O)(mes)3 is distorted tetrahedral with Ir=O and Ir-C bond lengths of 1.725(9) and 1.989-2.034(13) angstrom, respectively.

  DOI：

  10.1016/s0277-5387(00)81474-6

文献信息

• Ultrafast and Ultraslow Oxygen Atom Transfer Reactions between Late Metal Centers
  作者：Kevin C. Fortner、David S. Laitar、John Muldoon、Lihung Pu、Sonja B. Braun-Sand、Olaf Wiest、Seth N. Brown

  DOI：10.1021/ja065713h

  日期：2007.1.1

  exchange rates can be rationalized by an analogue of the inner-sphere reorganization energy. Both Ir(III) and Ir(V) are pyramidal and can form pyramidal iridium(IV) with little energetic cost in an orbitally allowed linear approach. Conversely, pyramidalization of the planar tris(imido)osmium(VI) fragment requires placing a pair of electrons in an antibonding orbital. The unique propensity of (mes)3Ir=O

  Oxotrimesityliridium(V), (mes)3Ir=O (mes = 2,4,6-trimethylphenyl) 和trimesityliridium(III), (mes)3Ir，在室温下经历极快的简并金属间氧原子转移。在低温下，这两种配合物会形成 (mes)3Ir-O-Ir(mes)3，其 2,6-二甲基苯基类似物已通过晶体学表征。mu-氧代二聚体解离速率的变温 NMR 测量值与低温光谱法的配比平衡测量值表明，铱 (V) 和铱 (III) 之间的氧原子交换以速率常数发生，外推到 20 摄氏度，5 x 107 M-1 s-1。oxotris(imido)osmium(VIII) 配合物 (ArN)3Os=O（Ar = 2,6-二异丙基苯基）也经历简并金属间原子转移到其脱氧伙伴，(ArN)3Os。然而，尽管其金属-氧键强度和对三苯基膦的反应性与 (mes)3Ir=O 几乎相同，锇络合物
• Stoichiometric and Catalytic Oxygen Activation by Trimesityliridium(III)
  作者：Bridey Grant Jacobi、David S. Laitar、Lihung Pu、Michael F. Wargocki、Antonio G. DiPasquale、Kevin C. Fortner、Stephany M. Schuck、Seth N. Brown

  DOI：10.1021/ic025700e

  日期：2002.9.1

  magnitude more slowly. Ir(mes)(3) binds PPh(3) reversibly (K(assoc) = 84 +/- 3 M(-1) in toluene at 20 degrees C) to form an unsymmetrical, sawhorse-shaped four-coordinate complex, whose temperature-dependent NMR spectra reveal a variety of dynamic processes. Oxygen atom transfer from (mes)(3)Ir=O and dioxygen activation by (mes)(3)Ir can be combined to allow catalytic aerobic oxidations of triphenylphosphine

  Trimesityliridium（III）（mesityl = 2,4,6-trimethylphenyl）与O（2）反应形成羰基三茂铁锂（V），（mes）（3）Ir = O，在铱中完全是二阶反应。与Wilkinson的最初报告相反，没有证据表明该反应中大量中间体的积累。含氧配合物（mes）（3）Ir = O在DeltaH ++ = 10.04 +/- 0.16 kcal / mol和DeltaS ++ = -21.6 +/- 0.5 cal /（mol.K）的二级反应中将三苯膦氧化为三苯膦氧化物在1,2-二氯乙烷中 三苯基ar也被氧化，尽管慢了一个数量级。Ir（mes）（3）可逆地结合PPh（3）（在20°C的甲苯中K（assoc）= 84 +/- 3 M（-1））形成不对称的锯齿形四坐标复合物，依赖温度的NMR光谱揭示了各种动态过程。（mes）（3）Ir = O的氧原子转移和（mes