[Cp*ethylIrCl]2(μ2-Cl)2 | 68678-63-7

• 英文名称: [Cp*ethylIrCl]2(μ2-Cl)2
• 英文别名: [(η-C5Me4Et)IrCl2]2；[Cp*^ethylIrCl]₂(μ²-Cl)₂；[(Cp^*ethyl)IrCl₂]₂；[^EtCp*IrCl(μ-Cl)]₂
• CAS: 68678-63-7
• 化学式: C₂₂H₃₄Cl₄Ir₂
• 分子量: 824.764
• InChiKey: UVDYJPSETRVEIU-UHFFFAOYSA-J

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：

  [Cp*ethylIrCl]2(μ2-Cl)2 、 bicyclo<3.2.1>octa-2,6-diene 在 sodium carbonate 作用下， 以 异丙醇 为溶剂， 反应 3.0h， 以74%的产率得到(η⁴-bicyclo[3.2.1]octa-2,6-diene)(η⁵-ethyltetramethylcyclopentadienyl)iridium
  参考文献：
  名称：

  d9 (Co, Rh, Ir) 和 d8 (Ru) 金属配位双环[3.2.1]octa-2,6-二烯中的碳-碳键通过 Aastic MHC 和 MH 相互作用活化

  摘要：

  这一贡献揭示了一系列 [M(η 5 -C 5 R 5 )(η 2 :η 2 -bicyclo[3.2.1]octa-2,6-diene or 2, 6-bcod)(M=Co, Rh, Ir, R=H, Me)] 1-3和[Ru(η 6 -芳烃)(η 2 :h 2 -bicyclo [3.2.1]octa-2,6 -二烯)(芳烃= C 6 Me 6 , C 6 Me 4 H 2 , C 6 H 3 Me 3 )] 4配合物。这些配位双环[3.2.1]octa-2,6-diene 或 2,6-bcod 配合物1,3,4与 HPF 6 (60% aq)、HBF 4等超强酸的单质子化。Et 2 O 或 CF 3 SO 3 H 在低温（-80° 至 -20 °C）下形成 [Rh(µ-H)(η 5 -C 5 R 5 )(η 2 :h 2 - 2,6-bcod)] + , 5 , [Co(µ-H)(h 5

  DOI：

  10.1016/j.jorganchem.2022.122349
• 作为产物：
  描述：

  bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 1,2,3,4-tetramethyl-5-ethyl-1,3-cyclopentadiene 在 盐酸 作用下， 以 甲醇 为溶剂， 115.0 ℃ 、1.03 MPa 条件下， 反应 1.0h， 以50%的产率得到[Cp*ethylIrCl]2(μ2-Cl)2
  参考文献：
  名称：

  快速获得衍生化的二聚环取代的二氯（环戊二烯基）铑（III）和铱（III）配合物

  摘要：

  The present work describes the design and synthesis of a series of rhodium and iridium dimers [(eta(5)-ring)MCl](2)(mu(2)-Cl)(2) (where (eta(5)-ring)MCl = (eta(5)-Me4C5R)Rh(III)Cl or (eta(5)-Me4C5R)Ir(III)Cl) using a new and efficient 1 h procedure. Rhodium and iridium dimeric complexes were synthesized via a microwave reaction. The modified HMe4C5R (R = isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, phenyl, benzyl, phenethyl, cyclohexyl, and cyclopentyl) type ligands were synthesized by reaction of 2,3,4,S-tetramethylcyclopent-2-en-1-one with the respective Grignard reagent (RMgX), followed by elimination of water under acidic conditions to produce the tetramethyl(alkyl or aryl)cyclopentadienes in moderate to excellent yields (40-98%). Reaction of the HMe4C5R ligands with [M(COD)](mu(2)-Cl)(2) (M = Rh, Ir; COD = 1,S-cyclooctadiene) gave the dimeric complexes [(eta(5)-Me4C5R)MCl](2)(mu(2)-Cl)(2) in yields ranging from 47% to 96%. The derivatized dimers were tested for antimicrobial activity, showing activity against Mycobacterium smegmatis and improved activity with derivatized R groups against Staphylococcus aureus and MRSA 43300. The characterization of these complexes was completed by NMR spectroscopy, single-crystal X-ray diffraction, high-resolution mass spectrometry, and elemental analysis.

  DOI：

  10.1021/acs.organomet.6b00580

文献信息

• Modulating the water oxidation catalytic activity of iridium complexes by functionalizing the Cp*-ancillary ligand: hints on the nature of the active species
  作者：Giordano Gatto、Alice De Palo、Ana C. Carrasco、Ana M. Pizarro、Stefano Zacchini、Guido Pampaloni、Fabio Marchetti、Alceo Macchioni

  DOI：10.1039/d0cy02306j

  日期：——

  A comparative study on the behavior of a series of iridium dimeric WOCs with modified Cp* ligands reveals the key role played by the variable substituent.

  一项关于一系列具有改性Cp*配体的铱二聚WOCs行为的比较研究揭示了可变取代基发挥的关键作用。
• Synthesis, Characterization, and Antimicrobial Activity of Rh^III and Ir^III β-Diketonato Piano-Stool Compounds
  作者：Christine M. DuChane、Loren C. Brown、Virginia S. Dozier、Joseph S. Merola

  DOI：10.1021/acs.organomet.7b00742

  日期：2018.2.26

  IrIII half-sandwich compounds of the type [(η5-Cp*R)M(β-diketonato)Cl] were synthesized and characterized, including 17 X-ray crystallographic structures. In general, the complexes were synthesized in short reaction times and in good yield. The antimicrobial properties of these complexes were tested against a variety of microbes, and several complexes were found to have good activity against Mycobacterium

  一系列的Rh的III和Ir III的类型的半夹心化合物[（η 5 -Cp * - [R）M（β-二酮盐）CL]被合成和表征，其中包括17 X射线晶体结构。通常，以短的反应时间和良好的产率合成配合物。测试了这些复合物对多种微生物的抗菌性能，发现几种复合物对耻垢分枝杆菌具有良好的活性。
• Iridium and Rhodium Complexes Containing Fluorinated Phenyl Ligands and Their Transformation to η²-Benzyne Complexes, Including the Parent Benzyne Complex IrCp*(PMe₃)(C₆H₄)
  作者：Russell P. Hughes、Roman B. Laritchev、Alex Williamson、Christopher D. Incarvito、Lev N. Zakharov、Arnold L. Rheingold

  DOI：10.1021/om0204787

  日期：2002.10.1

  yield. Similarly, treatment of RhCp*(CO)2 (7) with C6F5I in toluene at 80 °C affords a pentafluorophenyl complex of rhodium, RhCp*(C6F5)(CO)I (8). Treatment of 8 with PMe3 at room temperature affords RhCp*(C6F5)(PMe3)I (9), which reacts with NaBH4 to give RhCp*(C6F5)(PMe3)H (10). Treatment of 10 with n-BuLi gives the rhodium tetrafluorobenzyne complex RhCp*(η2-C6F4)(PMe3) (11) in high yield. Treatment

  用苯中的C 6 F 5 I在回流下处理IrCp *（CO）2（1），得到氧化加成产物IrCp *（C 6 F 5）（CO）I（2）。用PMe 3处理2得到IrCp *（C 6 F 5）（PMe 3）I（3），在痕量水存在下用AgO 3 SCF 3处理后，得到阳离子络合物[IrCp *（C 6 F 5）（PMe 3）（OH 2）] O 3 SCF 3（4）。用1,8-双（二​​甲基氨基）萘（质子海绵）处理4得到氢化物络合物IrCp *（C 6 F 5）（PMe 3）H（5），该化合物与n -BuLi反应生成四氟苯甲醛络合物IrCp *（η 2 -C 6 ˚F 4）（PME 3）（6以高收率）。同样，在80°C的甲苯中用C 6 F 5 I处理RhCp *（CO）2（7），得到铑的五氟苯基配合物RhCp *（C 6 F 5）（CO）I（8）。在室温下用PMe 3处理8得到RhCp *（C 6 F
• Cyclopentadienyl and Imide Ligand Transfer from Zirconium to Iridium:  Can Early Transition Metal Imido Compounds Be Used as Imide Transfer Reagents?
  作者：Patrick L. Holland、Richard A. Andersen、Robert G. Bergman

  DOI：10.1021/om970827a

  日期：1998.2.1

  Instead of leading to imido group transfer, treatment of [Cp*Ir(thf)3][OTf]2 with Cp2Zr(NtBu)(thf) (Cp* = C5Me5; Cp = C5H5) gave cyclopentadienyl transfer from Zr to Ir. To characterize the product of this type of reaction more completely, reaction of the corresponding ethyl-substituted compound [(C5Me4Et)Ir(thf)3][OTf]2 with the imidozirconium complex was also carried out. This led to [CpEtIrCp][

  代替导致亚氨基基团转移，用Cp 2 Zr（N t Bu）（thf）处理[Cp * Ir（thf）3 ] [OTf] 2（Cp * = C 5 Me 5 ; Cp = C 5 H 5）得到从Zr到Ir的环戊二烯基转移。为了更完全地表征这种反应的产物，还进行了相应的乙基取代的化合物[（C 5 Me 4 Et）Ir（thf）3 ] [OTf] 2与亚胺锆配合物的反应。这导致[Cp Et IrCp] [CpZr（NH t Bu）（OTf）3（thf）]，已经在晶体学上进行了表征。还对已知的五甲基铱iri盐[Cp * IrCp] [BF 4 ]进行了X射线研究。在相对于上述化学，反应的Cp 2 Zr的（N吨卜）（THF）给出了异双双（亚氨基）络合物的Cp *的Ir（μ-N吨丁基）2 ZrCp 2。因此，在这些反应中均未观察到亚氨基从锆中心转移。
• Synthesis, Characterization, and Antimicrobial Activity of Rh^III and Ir^III N-Heterocyclic Carbene Piano-Stool Complexes
  作者：Chad M. Bernier、Christine M. DuChane、Justin S. Martinez、Joseph O. Falkinham、Joseph S. Merola

  DOI：10.1021/acs.organomet.1c00166

  日期：2021.6.14

  and IrIII piano-stool complexes of the form [(η5-Cp*R)M(NHC)Cl2] was synthesized and characterized, including 12 X-ray crystallographic structures. The antimicrobial properties of these complexes were screened against a variety of microbes, with several achieving high activities, most notably against Mycobacterium smegmatis (MICs as low as 0.45 μM). In general, the Rh complexes were more potent than

  合成并表征了一系列[(η 5 -Cp* R )M(NHC)Cl 2 ]形式的 Rh III和 Ir III钢琴-凳配合物，包括 12 个 X 射线晶体结构。这些复合物的抗菌特性针对多种微生物进行了筛选，其中几种实现了高活性，最显着的是针对耻垢分枝杆菌（MIC 低至 0.45 μM）。一般来说，Rh 复合物比它们的 Ir 类似物更有效，并且活性随着 Cp* R和 NHC 配体的疏水性而增加。