[(η5-C5Me5)iridium(III)(2-(2-pyridyl)phenyl)(MeCN)]triflate | 1147996-87-9

• 英文名称: [(η5-C5Me5)iridium(III)(2-(2-pyridyl)phenyl)(MeCN)]triflate
• 英文别名: Cp*Ir(MeCN)(2-phenylpyridine)OTf；[(Cp*)Ir(ppy)(MeCN)]OTf；Cp*Ir(MeCN)(ppy)OTf
• CAS: 1147996-87-9
• 化学式: CF₃O₃S*C₂₃H₂₆IrN₂
• 分子量: 671.763
• InChiKey: LDRNWBBZEAQVKP-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：

  三乙基硅烷 、 [(η5-C5Me5)iridium(III)(2-(2-pyridyl)phenyl)(MeCN)]triflate 以 二氯甲烷 为溶剂， 反应 22.0h， 以56%的产率得到
  参考文献：
  名称：

  被困的Ir（III）硅烷催化中间体中供体-受体（Ir–H）→SiR3相互作用的证据

  摘要：

  The ionic iridacycle [(2-phenylenepyridine-kappa N,kappa C)-IrCp*(NCMe)][BArF24] ([2][BArF24]) displays a remarkable capability to catalyze the O-dehydrosilylation of alcohols at room temperature (0.4 x 10(3) < TON < 10(3), 8 x 10(3) < TOFi < 1.9 x 10(5) h(-1) for primary alcohols) that is explained by its exothermic reaction with Et3SiH, which affords the new cationic hydrido-Ir(III)-silylium species [3][BArF24]. Isothermal calorimetric titration (ITC) indicates that the reaction of [2][BArF24] with Et3SiH requires 3 equiv of the latter and releases an enthalpy of -46 kcal/mol in chlorobenzene. Density functional theory (DFT) calculations indicate that the therrnochemistry of this reaction is largely dominated by the concomitant bis-hydrosilylation of the released MeCN ligand. Attempts to produce [3][BF4] and [3][OTf] salts resulted in the formation of a known neutral hydrido-iridium(III) complex, i.e. 4, and the release of Et3SiF and Et3SiOTf, respectively. In both cases formation of the cationic p-hydrido-bridged bis-iridacyclic complexes [5][BF4] and [5][OTf], respectively, was observed. The structure of [5][OTf] was established by X-ray diffraction analysis. Conversion of [3] [BArF24] into 4 upon reaction with either 4-N,N-dimethylaminopyridine or [nBu(4)][OTf] indicates that the Ir center holds a +III formal oxidation state and that the Et3Si+ moiety behaves as a Z-type ligand according to Green's formalism. [3][BArF24], which was trapped and structurally characterized and its electronic structure investigated by state-of-the-art DFT methods (DFT-D, EDA, ETS-NOCV, QTAIM, ELF, NCI plots and NBO), displays the features of a cohesive hydridoiridium(III)-> silylium donor-acceptor complex. This study suggests that the fate of [3](+) in the O-dehydrosilylation of alcohols is conditioned by the nature of the associated counteranion and by the absence of Lewis base in the medium capable of irreversibly capturing the silylium species.

  DOI：

  10.1021/acs.organomet.6b00248
• 作为产物：
  描述：

  [Cp*Ir(ppy)OH₂][OTf] 、 乙腈 以 乙醚 、 乙腈 为溶剂， 生成 [(η5-C5Me5)iridium(III)(2-(2-pyridyl)phenyl)(MeCN)]triflate
  参考文献：
  名称：

  在环金属化铱（III）络合物的Ir- Cσ键中插入亚硝基和硫族油酸酯基团

  摘要：

  的治疗的[Cp *的Ir（ppy）CL]（CP * =η 5 -C 5我5，ppyH = 2-（2-吡啶基）苯基）有Ag（OTF）（OTF -  =三氟甲磺酸酯）在MeOH和MeCN，得到溶剂络合物[Cp * Ir（ppy）（solv）] [OTf]（solv = MeOH（1）和MeCN（2））。配合物1能够分别用PhIO和PhINTs（Ts =甲苯磺酰基）催化苯乙烯的氧化和叠氮化。的治疗2与PhINTs化学计量量导致插入的NT组进入铱- C（PPY）键和形成的[Cp *的Ir（η 2 -ppy-NTS）（MeCN中）] [光学传递函数（3）。用R 2 E处理12，得到的[Cp *的Ir（ppy）（η 1 -R 2 ë 2）] [光学传递函数（E = S（4），硒（5），碲（6））。的反应4和5有Ag（OTF）导致E-E键和插入的ER组入的Ir-C（PPY）键的裂解。复合物的晶体结构2 -

  DOI：

  10.1016/j.jorganchem.2010.02.002

文献信息

• Synthesis and oxidation of Cp*IrIII compounds: functionalization of a Cp* methyl group
  作者：Lisa S. Park-Gehrke、John Freudenthal、Werner Kaminsky、Antonio G. DiPasquale、James M. Mayer

  DOI：10.1039/b820839e

  日期：——

  [CpIrCl(2)](2) () and new CpIr(III)(L-L)X complexes (L-L = N-O or C-N chelating ligands; X = Cl, I, Me) have been prepared and their reactivity with two-electron chemical oxidants explored. Reaction of with PhI(OAc)(2) in wet solvents yields a new chloro-bridged dimer in which each of the Cp ligands has been singly acetoxylated to form [Cp(OAc)Ir(III)Cl(2)](2) () (Cp(OAc) = eta(5)-C(5)Me(4)CH(2)OAc).

  [CpIrCl（2）]（2）（）和新的CpIr（III）（LL）X配合物（LL = NO或CN螯合配体； X = Cl，I，Me）已经制备，并且它们与二电子化学反应探索氧化剂。在湿溶剂中与PhI（OAc）（2）反应产生新的氯桥二聚体，其中每个Cp配体均被单独乙酰氧基化以形成[Cp（OAc）Ir（III）Cl（2）]（2） （）（Cp（OAc）= eta（5）-C（5）Me（4）CH（2）OAc）。配合物和相关的羧基和烷氧基官能化的Cp（OR）配合物也可以由正（PhIO）（n）和ROH制备。[Cp（OAc）Ir（III）Cl（2）]（2）（）和甲氧基类似物[Cp（OMe）Ir（III）Cl（2）]（2）（）进行了结构表征。用2-苯基吡啶处理[CpIrCl（2）]（2）（）产生CpIr（III）（ppy）Cl（）（ppy =环金属化的2-苯基吡啶基），其很容易转化为其碘化物和甲基类似物CpIr（III）