Cp*2Ir2(μ-6,11-dihydroxy-5,12-naphthacenedione)Cl2 | 1190934-87-2

• 英文名称: Cp*2Ir2(μ-6,11-dihydroxy-5,12-naphthacenedione)Cl2
• 英文别名: Cp*2Ir₂(μ-6,11-dihydroxy-5,12-naphthacenedione)Cl₂；Cp*2Ir₂(μ-DHNA)Cl₂；[(iridium(C5H5(CH3)5)(chloride))2(μ-6,11-dihydroxy-5,12-naphthacenedione(-2H))]；[Cp*2Ir2(μ-6,11-dihydroxy-5,12-naphthacenequinone(2-))Cl2]；(C5Me5)2Ir2(μ-6,11-dioxy-5,12-naphthacenedione)Cl2；[(Ir(Cp*)Cl)2(dhnq)]
• CAS: 1190934-87-2
• 化学式: C₃₈H₃₈Cl₂Ir₂O₄
• 分子量: 1014.06
• InChiKey: AMUCFQUYGJPYJV-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*2Ir2(μ-6,11-dihydroxy-5,12-naphthacenedione)Cl2 、 silver trifluoromethanesulfonate 、 1,2-二(4-吡啶基)乙烯 以 甲醇 为溶剂， 以86%的产率得到[Cp*4Ir4(μ-E-1,2-bis(4-pyridyl)ethene)2(μ-6,11-dihydroxy-5,12-naphthacenequinone(2-))2](OTf)4
  参考文献：
  名称：

  Self-assembled half-sandwich Ir, Rh-based organometallic molecular boxes for reversible trapping of halocarbon molecules

  摘要：

  用碱处理[ Cp * MCl(μ-Cl)]2 (M = Ir 或 Rh)与6,11-二羟基-5,12-萘酮（H2DHNA）反应，得到相应的双核络合物[ Cp * 2M2(μ-DHNA)Cl2]（M = Ir (1a); M = Rh (1b)）。将1a或1b与双齿配体(L)，如吡嗪、4,4'-二吡啶(bpy)、E-1,2-双(4-吡啶)乙烯(bpe)或2,5-双(4-吡啶)-1,3,5-噁二唑(bpo)在CH3OH中与AgOTf（OTf = CF3SO3）一起处理，得到相应的四核络合物，通式为[ Cp * 4M4(μ-DHNA)2(μ-L)2](OTf)4 (3a, 4a, 5a, 6a: M = Ir; 3b, 4b, 5b, 6b: M = Rh)。对3a、3b、4a、4b、5a和5b的X射线分析表明，每个半三明治金属中心通过吡啶配体和双双齿桥联配体连接，构建出具有不同尺寸的矩形腔体，并且独立分子之间强烈的π-π相互作用形成了固态中的矩形通道。基于H2DHNA和吡嗪间隔配体的络合物3a和3b显示出选择性和可逆的小有机分子吸附特性。作为与单体络合物相互作用层的模板，C–H⋯Cl相互作用的例子被研究用于创建嵌插超分子阵列。

  DOI：

  10.1039/b925098k
• 作为产物：
  描述：

  bis[dichloro(pentamethylcyclopentadienyl)iridium(III)] 、 6,11-二羟基-5,12-萘并萘二酮 在 MeONa 作用下， 以 甲醇 为溶剂， 以93%的产率得到Cp*2Ir2(μ-6,11-dihydroxy-5,12-naphthacenedione)Cl2
  参考文献：
  名称：

  Self-assembled half-sandwich Ir, Rh-based organometallic molecular boxes for reversible trapping of halocarbon molecules

  摘要：

  用碱处理[ Cp * MCl(μ-Cl)]2 (M = Ir 或 Rh)与6,11-二羟基-5,12-萘酮（H2DHNA）反应，得到相应的双核络合物[ Cp * 2M2(μ-DHNA)Cl2]（M = Ir (1a); M = Rh (1b)）。将1a或1b与双齿配体(L)，如吡嗪、4,4'-二吡啶(bpy)、E-1,2-双(4-吡啶)乙烯(bpe)或2,5-双(4-吡啶)-1,3,5-噁二唑(bpo)在CH3OH中与AgOTf（OTf = CF3SO3）一起处理，得到相应的四核络合物，通式为[ Cp * 4M4(μ-DHNA)2(μ-L)2](OTf)4 (3a, 4a, 5a, 6a: M = Ir; 3b, 4b, 5b, 6b: M = Rh)。对3a、3b、4a、4b、5a和5b的X射线分析表明，每个半三明治金属中心通过吡啶配体和双双齿桥联配体连接，构建出具有不同尺寸的矩形腔体，并且独立分子之间强烈的π-π相互作用形成了固态中的矩形通道。基于H2DHNA和吡嗪间隔配体的络合物3a和3b显示出选择性和可逆的小有机分子吸附特性。作为与单体络合物相互作用层的模板，C–H⋯Cl相互作用的例子被研究用于创建嵌插超分子阵列。

  DOI：

  10.1039/b925098k

文献信息

• Extending Rectangular Metal-Organic Frameworks to the Third Dimension: Discrete Organometallic Boxes for Reversible Trapping of Halocarbons Occurring with Conservation of the Lattice
  作者：Ying-Feng Han、Wei-Guo Jia、Yue-Jian Lin、Guo-Xin Jin

  DOI：10.1002/anie.200805949

  日期：——

  Gone up in frames: Organometallic “molecular splints” with half‐sandwich Ir and Rh corners are synthesized, characterized, and studied for reversible trapping of halocarbons. Complex 1 (M=Ir, Rh) selectively recognizes CH2Cl2 and ClCH2CH2Cl molecules with retention of crystallinity. These complexes undergo reversible single‐crystal to single‐crystal structural transformations that are induced by solvent

  逐渐消失：合成，表征和夹带半夹心Ir和Rh角的有机金属“分子夹板”，并进行了可逆捕集卤化碳的研究。络合物 1（M ＝ Ir，Rh）选择性地识别具有结晶性的CH 2 Cl 2和ClCH 2 CH 2 Cl分子。这些复合物经历由溶剂交换引起的可逆的单晶至单晶结构转变。
• Syntheses and Reactions of Half-Sandwich Iridium, Rhodium, and Ruthenium Metallacycles Containing 4-Pyridyl Dithioether Ligands†Dedicated to Professor Kazuyuki Tatsumi on the occasion of his 60th birthday.
  作者：Ai-Quan Jia、Ying-Feng Han、Yue-Jian Lin、Guo-Xin Jin

  DOI：10.1021/om900921g

  日期：2010.1.11

  Metallacyclic complexes [CP4*Ir-4(mu-L')(2)(mu-L)(2)](OTf)(4) (2a, L' = 6,11-dioxy-5,12-naphthacencdione (dhnq(2-)); L = 4-pyridyl dithioether), [CP2*Rh-2(mu-L')(mu-L)](OTf)(2) (3b), and [(p-cymene)(2)Ru-2-(mu-L')(mu-L)](OTf)(2) (3c) were obtained by the reactions of CP2*M-2(mu-L')Cl-2 (M = Ir (1a), Rh (1b)) or (p-cymene)(2)Ru-2(mu-L')Cl-2 (1c) with a flexible bipyridine-based ligand (L) in the presence of AgOTf (OTf = CF3SO3). Treatments of tetranuclear complex 2a and binuclear complexes 3b and 3c with [Cp*IrCl](2)(OTf)(2) or [Cp*RhCl](2)(OTf)(2) gave the homotrinuclear complexes [Cp-3*Ir-3(mu-L')(mu-L)Cl]-(OTf)(3) (4a) and [CP3*Rh-3(mu-L')(mu-L)Cl](OTf)(3) (4b) and heterotrinuclear complexes [CP3*Ir2Rh-(mu-L')(mu-L)Cl](OTf)(3) (4c), [CP3*Rh2Ir(mu-L')(mu-L)Cl](OTf)(3) (4d), [Cp*)-p-cymene)(2)Ru2Ir(mu.-L')-(mu-L)Cl](OTf)(3) (4e), and [Cp*)-p-cymene)(2)Ru2Rh(mu-L')(mu-L)Cl](OTf)(3) (4f), respectively. The flexible tetranuclear complex 2a exhibited different conformations with different guest solvents. The complexes were characterized by IR, H-1 NMR spectroscopy, and elemental analysis. In addition, X-ray Structure analyses Were Performed oil ligand L and complexes 2a, 3c, 4a, and 4e.
• Synthesis, Characterization, and Properties of Half-Sandwich Iridium/Rhodium-Based Metallarectangles
  作者：Wen-Ying Zhang、Ying-Feng Han、Lin-Hong Weng、Guo-Xin Jin

  DOI：10.1021/om500338w

  日期：2014.6.23

  Tetranuclear half-sandwich iridium or rhodium complexes were obtained in good yields from the reactions of the binuclear half-sandwich metal precursors [Cp*M-2(2)(mu-CA)]Cl-2 (1a, M = Ir; 1b, M = Rh; CA = chloranilate) or [Cp*M-2(2)(mu-DHNA)]Cl-2 (2a, M = Ir; 2b, M = Rh; H(2)DHNA = 6,11-dihydroxynaphthacene-5,12-dione) with diPyNI (diPyNI = N,N-bis(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide) in the presence of AgOTf (OTf = CF3SO3) in CH3OH, respectively. The new metallarectangles have been characterized by elemental analysis, FT-IR, H-1 NMR, electrospray mass spectrometry (ESI-MS), and UV/vis absorption spectroscopy. The interactions of these metallarectangles with aromatic molecules, especially pyrene, in solution have been studied by various NMR techniques (1D, DOSY, and ROESY) and UV-vis absorption. DOSY measurements suggest that the interactions between metallarectangle 4a and pyrene are outside of the cavity. The strong pi center dot center dot center dot pi interactions between pyrene and the naphthalenetetracarboxydiimide ring of metallarectangle 4a were further supported by single-crystal X-ray diffraction data; pyrene molecules are found outside the cavity of the metallarectangle.
• Box-like Heterometallic Macrocycles Derived from Bis-Terpyridine Metalloligands
  作者：Jing-Jing Liu、Yue-Jian Lin、Guo-Xin Jin

  DOI：10.1021/om500093p

  日期：2014.3.10

  A series of [4+2] hexanuclear heterometallic macrocycles, [Cp*Ir-2(2)(mu-DHNA)](2)[Zn(pyterpy)(2)](2)(OTf)(2)}center dot(OTf)(6) (1a), [Cp*Ir-2(2)(mu-DHNA)](2)[Zn(pyterpy)(2)](2)}center dot(SbF6)(8) (1a'), [Cp*Rh-2(2)(mu-DHNA)](2)[Zn(pyterpy)(2)](2)}center dot(OTf)(8) (1b), [Cp*Ir-2(2)(mu-DHNA)](2)[Ni(pyterpy)(2)](2)(OTf)(2)}center dot(OTf)6 (2a), [Cp*Rh-2(2)(mu-DHNA)](2)[Ni(pyterpy)(2)](2)}center dot(OTf)(8) (2b), [Cp*Ir-2(2)(mu-DHNA)](2)[Cu(pyterpy)(2)](2)}center dot(PF6)(4)(OTf)(4) (3a), and [Cp*Rh-2(2)(mu-DHNA)](2)[Cu(pyterpy)(2)](2)}center dot(PF6)(4)(OTf)(4) (3b), have been constructed by the self-assembly of half-sandwich organometallic units [(Cp*M-2(2)(mu-DHNA)Cl-2] (M = Ir and Rh; Cp* = eta(5)-pentamethylcyclopentadienyl; DHNA = 6,11-dihydroxy-5,12-naphthacenedione) and the metalloligands [M(pyterpy)(2)](2+) (M = Zn, Ni, and Cu; pyterpy = 4'-(4-pyridyl)-2,2':6',2 ''-terpyridine). Confirmed by single-crystal X-ray analysis, complexes 1a-3b display hexanuclear heterometallic macrocycles with two box-like cavities. Interestingly, on the basis of the different combinations of metals, complexes 1a and 2a have the ability to encapsulate two OTf guest anions in the molecular cavities, but differ from that of the other complexes in which all counteranions exist outside the molecular backbones. In addition, the reaction of [Cp*MCl2](2) (M = Ir and Rh) and [Ni(pyterpy)(2)](NO3)(2) leads to the formation of [2+1] trinuclear heterometallic linear molecules Cp*2Ir2[Ni(pyterpy)(2)]Cl-4}(NO3)(2) (4a) and Cp*Rh-2(2)[Ni(pyterpy)(2)]Cl-4}(NO3)(2) (4b), which could be used as a kind of precursor.