[Ir2I4(μ-I)Me2(CO)4](1-) | 917704-61-1

• 英文名称: [Ir2I4(μ-I)Me2(CO)4](1-)
• CAS: 917704-61-1
• 化学式: C₆H₆I₅Ir₂O₄
• 分子量: 1161.07
• InChiKey: VSNOKYUXWLWUKN-UHFFFAOYSA-I

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：

  一氧化碳 、 [Ir2I4(μ-I)Me2(CO)4](1-) 以 not given 为溶剂， 生成 、 fac-IrI2Me(CO)3
  参考文献：
  名称：

  一氧化碳在均相催化反应中的活化：催化促进剂的性质和作用

  摘要：

  CO活化中的突出问题和挑战之一涉及对在许多均相催化的羰基化反应中使用的催化促进剂的作用缺乏详细的机械理解。这些问题及其解决方案的尝试，参考（i）已发现在合成催化剂中可用于从CO / H 2直接合成含氧化合物（例如乙二醇和乙醇）的复合催化剂中使用的促进剂种类繁多，（ii） N碱对烯烃催化甲氧基羰基化为酯的促进作用，以及（iii）一些初步的1313 C NMR光谱学证据可确定Ru促进剂作为Ir催化的甲醇羰基化成乙酸（乙酸）的碘化物抽象剂的双重作用。碘化物桥接的Ru-Ir二聚体的检测和溶液中的表征，正在促进建立合理的，内部一致的催化模型。

  DOI：

  10.1039/b107940a
• 作为产物：
  描述：

  碘化铟 、 cis,fac-[Ir(CO)2I₃Me]AsPh₄ 以 二氯甲烷 为溶剂， 生成 [Ir2I4(μ-I)Me2(CO)4](1-)
  参考文献：
  名称：

  Promotion of Iridium-Catalyzed Methanol Carbonylation:  Mechanistic Studies of the Cativa Process

  摘要：

  The iridium/iodide-catalyzed carbonylation of methanol to acetic acid is promoted by carbonyl complexes of W, Re, Ru, and Os and simple iodides of Zn, Cd, Hg, Ga, and In. Iodide salts (Lil and Bu4NI) are catalyst poisons. In situ IR spectroscopy shows that the catalyst resting state (at H2O levels greater than or equal to 5% w/w) is fac,cis-[Ir(CO)(2)I3Me](-), 2. The stoichiometric carbonylation of 2 into [Ir(CO)(2)I-3(COMe)]-, 6, is accelerated by substoichiometric amounts of neutral promoter species (e.g., [Ru(CO)(3)I-2)(2), [Ru(CO)(2)I-2](n), InI3, GaI3, and ZnI2). The rate increase is approximately proportional to promoter concentration for promoter: Ir ratios of 0-0.2. By contrast anionic Ru complexes (e.g., [Ru(CO)(3)I-3](-), [Ru(CO)(2)I-4](2-)) do not promote carbonylation of 2 and BU4NI is an inhibitor. Mechanistic studies indicate that the promoters accelerate carbonylation of 2 by abstracting an iodide ligand from the Ir center, allowing coordination of CO to give [Ir(CO)(3)I2Me], 4, identified by high-pressure IR and NMR spectroscopy. Migratory CO insertion is ca. 700 times faster for 4 than for 2 (85 degreesC, PhCI), representing a lowering of DeltaG(+/-) by 20 kJ mol(-1). Ab initio calculations support a more facile methyl migration in 4, the principal factor being decreased pi-back-donation to the carbonyl ligands compared to 2. The fac,cis isomer of [Ir(CO)(2)I-3(COMe)](-), 6a (as its Ph4As+ salt), was characterized by X-ray crystallography. A catalytic mechanism is proposed in which the promoter [M(CO)(m)I-n] (M = Ru, In; m = 3, 0; n = 2, 3) binds I- to form [M(CO)(m)In+1]-H3O+ and catalyzes the reaction HI(aq) + MeOAc --> Mel + HOAc. This moderates the concentration of HI(aq) and so facilitates catalytic turnover via neutral 4.

  DOI：

  10.1021/ja039464y

文献信息

• Analysis of the Synergistic Effect of Carbonylplatinum Complexes on the Iridium‐Catalysed Carbonylation of Methanol to Acetic Acid
  作者：Samuel Gautron、Nicolas Lassauque、Carole Le Berre、Philippe Serp、Laurent Azam、Roberto Giordano、Gábor Laurenczy、Daniel Thiébaut、Philippe Kalck

  DOI：10.1002/ejic.200500931

  日期：2006.3

  investigations into the promoting role of dicarbonyldiiodoplatinum complex in the iridium-catalysed carbonylation of methanol to acetic acid are consistent with iodide abstraction from the [IrI3(CH3)(CO)2]– resting state species by [PtI2(CO)2], unbolting the rate-limiting migratory CO insertion step. A new [Ir–Pt] heterodimetallic complex, which presumably represents the key species involved in the abstraction

  对二羰基二碘铂配合物在铱催化甲醇羰基化为乙酸中的促进作用的高压 NMR 机理研究与 [IrI3(CH3)(CO)2]– [PtI2(CO)2]-静息态物质中的碘化物提取一致)2]，解开限速迁移 CO 插入步骤。一种新的 [Ir-Pt] 异质二金属配合物，可能代表了参与提取 I- 的关键物质，已通过 NMR 和 FAB-MS 进行了表征。