[Ir(COD)OEt]2 | 35429-65-3

• 英文名称: [Ir(COD)OEt]2
• 英文别名: bis(η4-1,5-cyclooctadiene)di-μ-ethanoatodiiridium(I)；bis[μ-ethoxy(1,5-cyclooctadiene)-iridium(I)]；[Ir(COD)OEt]₂；[Ir(1,5-cyclooctadiene)(μ-OEt)]2；[Ir(μ-OEt)(cyclooctadiene)]2；[(1,5-cyclooctadiene)Ir(OEt)]2；[Ir(1,5-cyclooctadiene)(OEt)]2
• CAS: 35429-65-3
• 化学式: C₂₀H₃₄Ir₂O₂
• 分子量: 690.929
• InChiKey: RJNKSKHCEFSWKI-MIXQCLKLSA-N

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：

  [Ir(COD)OEt]2 、 4-[(3-Methyl)-1-imidazolio]benzolsulfonat 以 乙醇 、 水 为溶剂， 反应 72.0h， 生成 Na[Ir(NHC-PhSO3)₂(cod)]
  参考文献：
  名称：

  用于甘油转化为乳酸的新一代水溶性均相催化剂

  摘要：

  甘油增值的一种有吸引力的方法是催化转化为乳酸。通过克服与该反应的已知均相催化剂相关的溶解度挑战，我们表明具有磺酸盐官能化的翼尖的热稳健的Ir（I），Ir（III）和Ru（II）N-杂环卡宾（NHC）配合物非常多产对于该方法，除了碱水溶液外，不需要助溶剂。在常规加热和微波条件下都比较了催化剂的活性。活性最高的催化剂的TOF为45 592 h –1（微波）和3477 h –1（常规）中加入1当量的KOH，并以恒定速率进行至少8小时。尽管使用KOH观察到较高的活性，但该催化剂在较弱的碱K 2 CO 3（13000 h –1并同时形成甲酸）的情况下也具有很高的活性。可以修改方案以仅在3小时内实现甘油的定量转化。与非磺化类似物相比，这些催化剂的高活性归因于乳酸产物在水性介质中的稳定性。活性最高的催化剂对粗甘油保持相同的活性。对于活性最高的催化剂前体，提出了一种机制，涉及到O–H氧化氧化甘油。

  DOI：

  10.1021/acs.organomet.8b00081
• 作为产物：
  描述：

  bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 potassium ethoxide 以 neat (no solvent) 为溶剂， 生成 [Ir(COD)OEt]2
  参考文献：
  名称：

  从纯离子液体直接原位合成阳离子N-杂环卡宾铱和铑配合物：在环辛二烯催化脱氢中的应用

  摘要：

  从纯二烷基咪唑鎓离子液体（ILs）中发现了铑和铱的阳离子N-杂环卡宾（NHC）络合物的直接合成途径。该方法使用带有碱性阴离子配体[M（COD）（PPh 3）X]，X = OEt，MeCO 2的络合物，它们在不存在外部碱的情况下与灭活的咪唑鎓阳离子反应，生成一个M-NHC部分和游离的质子化的基地。这种新的一锅法合成方法留下纯净的，具有催化活性的IL溶液，比这类NHC配合物的传统合成方法更快，更清洁，更高效。观察到的反应性还使人们了解了在普通的二烷基咪唑类ILs中进行的铑和铱催化的NHC结合反应。

  DOI：

  10.1016/j.jorganchem.2008.04.017

文献信息

• Rhodium(i) and iridium(i) complexes of pyrazolyl-N-heterocyclic carbene ligands
  作者：Barbara A. Messerle、Michael J. Page、Peter Turner

  DOI：10.1039/b603455a

  日期：——

  Several Rh(I) and Ir(I) complexes containing an N-heterocyclic carbene-pyrazolyl chelate ligand have been synthesised. Determination of the single-crystal X-ray structure of the Ir(I) complex showed a novel binding mode with the iridium centre coordinated to two ligands via two carbene donors in preference to one ligand forming the entropically favoured chelate. The hydrogenation activity of several

  已合成了几种含有N-杂环卡宾-吡唑基螯合物的Rh（I）和Ir（I）配合物。Ir（I）配合物的单晶X射线结构的测定显示出一种新颖的结合模式，其中铱中心通过两个卡宾供体与两个配体配位，而不是一个配位体形成了熵有利的螯合物。研究了其中几种配合物的氢化活性，以及​​先前合成的含类似膦-吡唑基螯合物的Rh（I）和Ir（I）配合物的氢化活性。
• Construction of trinuclear iridium clusters through ancillary ortho-carborane-1,2-diselenolato ligands, with simultaneous iridium-induced B–H activation
  作者：Shuang Liu、Jian-Qiang Wang、Lin-Hong Weng、Guo-Xin Jin

  DOI：10.1039/b705366e

  日期：——

  The reaction of the 16-electron “pseudo-aromatic” complex Cp*Ir[Se2C2(B10H10)] (1, Cp* = η5-C5Me5) with [Ir(cod)(µ-OC2H5)]2 leads to the trinuclear iridium complexes (cod)Ir[Se2C2(B10H8)(OC2H5)]}Ir[Se2C2(B10H10)]IrCp*} (2), (cod)Ir[Se2C2(B10H8)(OC2H5)]}Ir[Se2C2(B10H9)]IrCp*} (3), Cp*Ir[Se2C2(B10H9)]}IrSe2[C2(B10H9)(OC2H5)]}[Se2C2(B10H10)] IrCp*} (4) and one mononuclear complex Cp*Ir[Se2C2(B10H8)(OC2H5)2] (5). The reactivity of 2 was investigated and revealed that transformation from 2 to 3 occurred thermally in solution. The transoid complex 2 (with the carborane diselenolato units in trans position) can be converted in nearly 90% yield to the cisoid complex 3. In complexes 2, 3, two diselenolato carborane ligands bridge the Ir3 core, which consists of Ir–Ir metal bonds. Compared with transoid 2, the cisoid 3 contains two iridium–boron bonds. Complex 4 consists of three different coordination environment carborane ligands (Ir–Bcluster: Cp*Ir[Se2C2(B10H9)]}, O–Bcluster: [Se2C2(B10H9)](OC2H5)}, and intact carborane: Cp*Ir[Se2C2 (B10H10)]}) without the presence of a metal–metal bond. Analogous reaction of 1 with [Ir(cod)(µ-OCH3)]2 results in formation of the trinuclear complex Cp*Ir[Se2C2(B10H9)]}IrSe2[C2(B10H9)(OCH3)]}[Se2C2(B10H10)]IrCp*} (6) and mononuclear complex Cp*Ir[Se2C2(B10H8)(OCH3)2] (7). The structures of 2, 3, 4, 5, 6 and 7 have been determined by crystallographic studies.

  16 电子 – 伪芳香族 – 配合物 Cp*Ir[Se2C2(B10H10)] (1, Cp* = η5-C5Me5) 与 [Ir(cod)(µ-OC2H5)]2 的反应产生三核铱配合物 (cod)Ir[Se2C2(B10H8)(OC2H5)]}Ir[Se2C2(B10H10)]IrCp*} (2), (cod)Ir[Se2C2(B10H8)(OC2H5)] }Ir[Se2C2(B10H9)]IrCp*} (3), Cp*Ir[Se2C2(B10H9)]}IrSe2[C2(B10H9)(OC2H5)]}[Se2C2(B10H10)] IrCp*} ( 4) 和一个单核配合物 Cp*Ir[Se2C2(B10H8)(OC2H5)2] (5)。对2的反应性进行了研究，发现在溶液中发生了从2到3的热转变。反式配合物 2（碳硼烷二硒醇单元处于反位）可以以近 90% 的收率转化为顺式配合物 3。在配合物 2、3 中，两个二硒醇碳硼烷配体桥接 Ir3 核心，该核心由 Ir–Ir 组成金属键。与反式2相比，顺式3含有两个铱-硼键。配合物4由三种不同配位环境的碳硼烷配体（Ir-B簇：Cp*Ir[Se2C2(B10H9)]}、O-B簇：[Se2C2(B10H9)](OC2H5)}和完整的碳硼烷： Cp*Ir[Se2C2 (B10H10)]})，不存在金属-金属键。 1 与 [Ir(cod)(µ-OCH3)]2 的类似反应导致形成三核配合物 Cp*Ir[Se2C2(B10H9)]}IrSe2[C2(B10H9)(OCH3)]}[Se2C2 (B10H10)]IrCp*} (6) 和单核复合物 Cp*Ir[Se2C2(B10H8)(OCH3)2] (7)。 2、3、4、5、6和7的结构已通过晶体学研究确定。
• Alkoxy/siloxy group exchange in the system vinyltrialkoxysilane–iridium(<scp>i</scp>) siloxide complex
  作者：Ireneusz Kownacki、Bogdan Marciniec、Maciej Kubicki

  DOI：10.1039/b208603b

  日期：——

  A study of reactions of dimeric siloxide iridium complex, [(cod)Ir(μ-OSiMe3)}2] (1) with vinyltriethoxysilane and vinyltrimethoxysilane has revealed a new type of the reaction—alkoxy group transfer from silicon to iridium with a simultaneous transfer of a siloxy group from iridium to silicon—as a result of which vinyldialkoxytrimethyldisiloxane and dimeric alkoxide iridium complex [(cod)Ir(μ-OR)}2] (3) are formed. The structure of [(cod)Ir(μ-OEt)}2] (3a) has been solved by X-ray diffraction.

  (cod)Ir(δ-OSiMe3)}2](1)与乙烯基三乙氧基硅烷和乙烯基三甲氧基硅烷的反应揭示了一种新的反应类型：烷氧基基团从硅转移到铱，同时硅氧基基团从铱转移到硅，由此形成乙烯基二甲氧基三甲基二硅氧烷和二聚烷氧基铱络合物[(cod)Ir(δ-OR)}2](3)。通过 X 射线衍射解决了[(cod)Ir(δ-OR)}2] (3a) 的结构问题。
• The fluorine-NHC gauche effect: a structural and computational study
  作者：Susann Paul、W. Bernd Schweizer、Graham Rugg、Hans Martin Senn、Ryan Gilmour

  DOI：10.1016/j.tet.2013.02.071

  日期：2013.7

  Herein, we report the synthesis and X-ray structural analysis of a collection of fluorinated metal N-heterocyclic carbenes (Ag, Au, Pd, Rh, Ir) and their precursor salts. The common structural feature of these species is a flanking fluoroethyl group, which is either freely rotating or embedded within a bicyclic framework. Solid state analysis confirmed a gauche conformational preference in all cases with the fluorine adopting a syn clinal arrangement (phi([NCCF])similar to 60 degrees) with respect to the triazolium nitrogen at the vicinal position of the NHC. A density functional theory analysis was employed to quantify these effects and evaluate the influence of electronic modulation of the carbenic carbon [(C=N+); neutral carbene (C:); metal-bound carbene (C=M)], on the relative gauche/anti preference, thus highlighting the potential of this conformational phenomenon as a useful molecular design strategy for controlling the topology of organometallic complexes. (C) 2013 Elsevier Ltd. All rights reserved.
• Iridium Complexes with <i>N</i>-Allyl-Substituted Benzimidazol-2-ylidene Ligands and Their Application in Catalytic Transfer Hydrogenation
  作者：F. Ekkehardt Hahn、Christian Holtgrewe、Tania Pape、Marta Martin、Eduardo Sola、Luis A. Oro

  DOI：10.1021/om0500873

  日期：2005.4.1

  The reactions of [Ir(mu-OMe)(cod)](2) with the N-allyl-substituted benzimidazolium salts 1-methyl-3-(2-propenyl)benzimidazolium iodide (2) and 1,3-di(2-propenyl)benzimidazolium bromide (3) have been found to afford the five-coordinated Ir(I) complexes [IrX(cod)(eta(2)-C-NHC)] (X = I, NHC = 1-methyl-3-(2-propenyl)benzimidazol-2-ylidene, 4; X = Br, NHC = 1,3-di(2-propenyl)benzimidazol-2-ylidene, 5), respectively. The cationic derivative [Ir(cod)(eta(2):eta(2)-C-NHC)]BF4 (NHC = 1,3-di(2-propenyl)benzimidazol-2-ylidene, 6), which contains an iridium center exclusively coordinated by sp(2) carbon atoms, has been prepared by treatment of 5 with AgBF4. The reaction between [Ir(mu-Cl)(cod)](2) and 3 in ethanol, in the presence of excess NaOEt, has allowed the synthesis of the four-coordinate complex [IrBr(cod)(C-NHC)] (NHC = 1,3-di(propyl)benzimidazol-2-ylidene, 7) after deprotonation of 3 and hydrogenation of both N-allyl substituents. The compounds 5, 6, and 7 have been characterized by X-ray diffraction. The neutral complexes 4, 5, and 7 have been tested as catalysts in the transfer hydrogenation of cyclohexanone using 2-propanol as hydrogen source. The catalytic reactions using 4 and 5 have been observed to progress without hydrogenation of the allyl substituents.