[Cp*₂Ir₂(μ-η⁴-C₂O₄)]Cl₂ | 280742-17-8

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: [Cp*₂Ir₂(μ-η⁴-C₂O₄)]Cl₂
• 英文别名: [{IrCl(Cp*)}2(μ-η²-η²-C₂O₄)]；[Cp*2Ir2(μ-η2-η2-C2O4)Cl2]；Ir2(C5(Me)5))2Cl2(μ-oxalato)；[(C5Me5)2Ir2(μ-C2O4)Cl2]；iridium(3+);oxalate;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;dichloride
• CAS: 280742-17-8
• 化学式: C₂₂H₃₀Cl₂Ir₂O₄
• 分子量: 813.824
• InChiKey: LKZAVKGCQINEBN-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  -3.62
• 重原子数：
  30
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  [Cp*₂Ir₂(μ-η⁴-C₂O₄)]Cl₂ 、 2,4,6-trimereaptotriazine, trisodium salt, nonahydrate 以 二氯甲烷 为溶剂， 以89%的产率得到[(C5Me5)3Ir3(μ3-1,3,5-triazine-2,4,6-trithiolato)Cl3]
  参考文献：
  名称：

  的半夹心配合物的合成，表征，和降冰片烯的聚合行为的[Cp * 3中号3（μ 3 -L）氯3 ]和混合[Cp * M（2- SPyH）氯2 ]（M = IR，M =铑，[L] 3− = 1,3,5-三嗪-2,4,6-三硫代巯基，2-SPy = 2-吡啶硫酮）

  摘要：

  三核配合物的[Cp * 3中号3（μ 3 -L）氯3 ]（3a中，M =铱;图3b，M = RH; [L] -3- = 1,3,5-三嗪-2,4,6- -trithiolato）已经通过桥接的反应合成草酸根络合物的[Cp * 2中号2（μ-C 2 ö 4）氯2 ]（图2a，M =铱;图2b，M = RH）为1的三钠盐，3,5-三嗪-2,4,6-三硫醇（Na 3 L）。半三明治铱和铑配合物[Cp * MCl（μ-Cl）] 2的反应用2-吡啶硫酮与β-吡啶并得到相应的单核络合物[Cp * M（2-SPyH）Cl 2 ]（4a，M ＝ Ir；4b，M ＝ Rh）。所有配合物均已通过元素分析，核磁共振和红外光谱进行了表征。3a，b和4a，b的分子结构已经通过X射线晶体学确定。三核铱配合物3a在甲基铝氧烷（MAO）作为助催化剂的存在下显示出降冰片烯聚合的催化活性。

  DOI：

  10.1021/om7010003
• 作为产物：
  描述：

  bis[dichloro(pentamethylcyclopentadienyl)iridium(III)] 、 silver oxalate 以 四氢呋喃 、 乙腈 为溶剂， 以87%的产率得到[Cp*₂Ir₂(μ-η⁴-C₂O₄)]Cl₂
  参考文献：
  名称：

  Studies of the Synthesis and Thermochemistry of Coordinatively Unsaturated Chelate Complexes (η⁵-C₅Me₅)IrL₂ (L₂ = TsNCH₂CH₂NTs, TsNCH₂CO₂, CO₂CO₂)

  摘要：

  A comparative synthetic, structural, and thermochemical study on a series of chelate complexes containing the fragment (eta(5)-C5Me5)Ir [(eta(5)-C5Me5)Ir(TsNCH2CH2NTs) (1), (eta(5)-C5Me5)Ir(TsNCH2CO2) (2), (eta(5)-C5Me5)Ir(CO2CO2) (3)] was performed to clarify the roles of carboxylato and sulfonamido ligands. Whereas 1 and 2 are monomeric in solution and in the solid state, 3 appears to exist as an oligomer or polymer, (3)(n), which can be broken up by addition of a Ligand L such as a phosphine, CO, or 2-methoxypyridine to form (eta(5)-C5Me5)Ir(L)(CO2CO2) (6). The synthesis of (3), from [(eta(5)-C5Me5)IrCl(mu-Cl)](2) required the use of silver oxalate in CH3CN, but if other solvents were used, the bridging oxalato complex (eta(5)-C5Me5)IrCl(mu-eta(2)-eta(2)-C2O4)ClIr(eta(5)-C5Me5) (7) was obtained and identified by X-ray diffraction. Enthalpies for reaction of THF-soluble monomers 1 and 2 with PMe3 were determined to be -28.7(0.5) and -28.5(0.4) kcal mol(-1), respectively. The oligomerization behavior of 3 may be a result of reduced sigma- or pi-donation of carboxylato ligands compared to N-tosylamido ligands, because the values for nu(CO) in oxalato and bissulfonamido complexes 6-CO and (eta(5)-C5Me5)Ir(CO)(TsNCH2CH2NTs) (4-CO) were 2064 and 2042 cm(-1), respectively.

  DOI：

  10.1021/ic990870l

文献信息

• Template-controlled topochemical photodimerization based on “organometallic macrocycles” through single-crystal to single-crystal transformation
  作者：Ying-Feng Han、Yue-Jian Lin、Wei-Guo Jia、Guo-Liang Wang、Guo-Xin Jin

  DOI：10.1039/b717554j

  日期：——

  Organometallic macrocycles 2a and 2b undergo [2 + 2] photochemical cycloaddition to form 3a and 3b in quantitative yield, accompanied by a single-crystal to single-crystal transformation.

  金属有机大环化合物2a和2b经历[2 + 2]光化学环加成反应，以定量产率生成3a和3b，伴随单晶到单晶的转化。
• Mixed-Metal Coordination Cages Constructed with Pyridyl-Functionalized β-Diketonate Metalloligands: Syntheses, Structures and Host-Guest Properties
  作者：Ying-Ying Zhang、Long Zhang、Yue-Jian Lin、Guo-Xin Jin

  DOI：10.1002/chem.201502194

  日期：2015.10.12

  and synthesis of mixed‐metal coordination cages, which can act as hosts to encapsule guest molecules, is a subject of intensive research, and the utilization of metalloligand is an effective method to construct a designed heterometallic architecture. Herein, a series of heterometallic cages with half‐sandwich Rh, Ir and Ru fragments using CuII‐metalloligand as a building block by a stepwise approach

  可以充当胶囊客体分子宿主的混合金属配位笼的设计与合成是一项深入研究的课题，金属配体的利用是构建设计的异金属结构的有效方法。在本文中，报道了一系列使用Cu II-金属配体作为分步结构的，具有半夹心Rh，Ir和Ru片段的杂金属笼。笼子的空腔大小可以通过有机配体的长度容易地控制。由于草酸盐基笼中的金属配体有些扭曲且呈凹形，因此分子中的Cu⋅⋅⋅O相互作用较弱，形成了双核铜单元。通过使用较长的配体2,5-二氯-3,6-二羟基-1,4-苯醌（H 2CA），有机金属盒显示出有趣的宿主-客体行为，这种行为足够大以容纳一些大分子，例如pyr和[Pt（acac）2 ]。有趣的是，在吡嗪存在下，具有较大腔体尺寸的杂金属笼可以转移到均金属六核棱柱体中。
• Stepwise formation of “organometallic boxes” with half-sandwich Ir, Rh and Ru fragments
  作者：Ying-Feng Han、Yue-Jian Lin、Lin-Hong Weng、Heinz Berke、Guo-Xin Jin

  DOI：10.1039/b711809k

  日期：——

  Octanuclear complexes with half-sandwich Ir, Rh and Ru fragments and tetra(4-pyridyl)porphyrin (L1) and oxalate (L2) spacer ligands [(Cp*M)4L1]2[L2]4 (M = Ir (6a) M = Rh (6b)), [((cymene)Ru)4(L1)]2[L2]4 were prepared and characterized.

  制备并表征了具有半三明治 Ir、Rh 和 Ru 片段以及四（4-吡啶基）卟啉（L1）和草酸盐（L2）间隔配体 [(Cp*M)4L1]2[L2]4 （M = Ir (6a) M = Rh (6b)）、[((亚甲基)Ru)4(L1)]2[L2]4 的八核配合物。
• Construction of half-sandwich rhodium- and iridium-based metallamacrocycles with different space conformations via isomeric pyridyl-substituted ligands
  作者：Yu-Xin Deng、Hai-Ning Zhang、Yue-Jian Lin、Guo-Xin Jin

  DOI：10.1080/00958972.2018.1461849

  日期：2018.7.3

  utilization of isomeric pyridyl-substituted ligands featuring different coordination vectors to rationally design and construct a series of discrete organometallic assemblies with specific space conformations. In the case of tetranuclear macrocycles constructed from the ligand 3-bpb, different conformations of these assemblies with C2v and C2 h point symmetry were revealed by single-crystal X-ray diffraction

  摘要在此，我们描述了利用具有不同配位载体的异构吡啶基取代配体来合理设计和构建一系列具有特定空间构象的离散有机金属组件。在由配体 3-bpb 构建的四核大环的情况下，通过单晶 X 射线衍射揭示了这些具有 C2v 和 C2h 点对称性的组件的不同构象。这些配合物通过 X 射线晶体学、1H NMR、DOSY NMR、IR 光谱和元素分析进一步表征。
• Stepwise Formation of Tetra- and Hexanuclear Iridium and Rhodium Complexes Containing Oxalato Ligands
  作者：Ying-Feng Han、Yue-Jian Lin、Wei-Guo Jia、Lin-Hong Weng、Guo-Xin Jin

  DOI：10.1021/om700691u

  日期：2007.11.1

  [Cp*2Rh2(μ-η2-η2-C2O4)Cl2] 2b with bidentate ligands such as 4,4‘-bipyridine (bpy) and 2,5-bis(4-pyridyl)-1,3,5-oxadiazole (bpo) in the presence of AgOTf gave the corresponding tetranuclear complexes [Cp*4M4(μ-L)2(μ-η2-η2-C2O4)2](OTf)4 (3a:  M = Ir, L = bpy; 3b:  M = Rh, L = bpy; 4a:  M = Ir, L = bpo; 4b:  M = Rh, L = bpo). The reactions of 2a and 2b with tridentate ligand 2,4,6-tri(4-pyridyl)-1,3,5-triazine

  的反应中的[Cp * 2的Ir 2（μ-η 2 - η 2 -C 2 ö 4）氯2 ]图2a和的[Cp * 2的Rh 2（μ-η 2 - η 2 -C 2 ö 4）氯2 ]图2b与二齿配位体如4,4'-联吡啶（BPY）和2,5-二中的AgOTf存在（4-吡啶基）-1,3,5-恶二唑（BPO），得到相应的四核配合物的[Cp * 4中号4（μ-L）2（μ-η 2 - η 2-C 2 O 4）2 ]（OTf）4（3a：M = Ir，L = bpy; 3b：M = Rh，L = bpy; 4a：M = Ir，L = BPO; 4b：M = Rh，L = BPO）。的反应图2a和2b中具有三齿中的AgOTf存在配体的2,4,6-三（4-吡啶基）-1,3,5-三嗪（TPT），得到相应的六核配合物的[Cp * 6中号6（μ -TPT）2（μ-η 2 - η 2 -C 2 ö 4）3 ]（OTF）6（图5a：M