[(κ3-C6H3-2,6-[CH2P(t-Bu)2]2)Ir(tert-butylvinyl)(H)] | 312960-77-3

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: [(κ3-C6H3-2,6-[CH2P(t-Bu)2]2)Ir(tert-butylvinyl)(H)]
• 英文别名: (2,6-C6H3(CH2P(t-Bu)2)2)IrH(trans-2-[tert-butyl]vinyl)；(PCP)IrH(trans-2-[tert-butyl]vinyl)；(η3-2,5-(t-Bu2PCH2)2C6H3)IrH(CH=CHBu-t)
• CAS: 312960-77-3
• 化学式: C₃₀H₅₅IrP₂
• 分子量: 669.934
• InChiKey: XSTPVXTZBFCNLM-UHFFFAOYSA-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：

  [(κ3-C6H3-2,6-[CH2P(t-Bu)2]2)Ir(tert-butylvinyl)(H)] 在 降冰片烯 作用下， 以 对二甲苯 为溶剂， 反应 5.0h， 生成
  参考文献：
  名称：

  铱络合物对醚、酯和甲苯磺酸酯 C(sp3)-O 键的裂解，由 C-H 键的氧化加成引发。实验和计算研究

  摘要：

  发现钳形连接的铱络合物 (PCP)Ir (PCP = κ(3)-C6H3-2,6-[CH2P(t-Bu)2]2) 发生 C(sp(3) )-O 键的甲酯 (CH3-O2CR')、甲苯磺酸甲酯 (CH3-OTs) 和某些缺电子的甲基芳基醚 (CH3-OAr)。DFT 计算和机理研究表明，反应是通过 CH 键的氧化加成和氧化物迁移进行的，而不是通过直接添加 CO 进行。因此，甲基芳基醚通过添加甲氧基 CH 键进行反应，然后 α-芳基氧化物迁移得到顺式-(PCP)Ir(H)(CH2)(OAr)，然后铱到亚甲基氢化物迁移得到（ PCP)Ir(CH3)(OAr)。乙酸甲酯在甲氧基上发生 CH 键加成得到 (PCP)Ir(H)[κ(2)-CH2OC(O)Me]，然后得到 (PCP-CH2)Ir(H)(κ(2)-O2CMe ) (6-Me) 其中甲氧基 CO 键已被裂解，来自甲氧基的亚甲基已迁移到 PCP

  DOI：

  10.1021/ja312464b
• 作为产物：
  描述：

  3,3-二甲基-1-丁烯 、 [(1,3-bis((di-tert-butylphosphino)methyl)benzene(-1H))IrH2] 以 1,2,5-trimethyl-benzene 为溶剂， 生成 [(κ3-C6H3-2,6-[CH2P(t-Bu)2]2)Ir(tert-butylvinyl)(H)]
  参考文献：
  名称：

  Mechanism of Alkane Transfer-Dehydrogenation Catalyzed by a Pincer-Ligated Iridium Complex

  摘要：

  The mechanism of (PCP)Ir-catalyzed transfer-dehydrogenation has been elucidated for the prototypical substrate/acceptor couple, COA/TBE, at 55 degrees C (COA = cyclooctane; TBE = tert-butylethylene). The catalytic cycle may be viewed as the sum of two reactions: (i) hydrogenation of TBE by (PCP)IrH2 and C-H addition of a second mole of TBE to give (PCP)IrH(tert-butylvinyl), and (ii) dehydrogenation of COA by (PCP)IrH(tert-butylvinyl) to give (PCP)IrH2, COE, and TBE. These two stoichiometric reactions have been observed independently and their kinetics determined. The overall catalysis has also been monitored in situ, and (PCP)IrH2 and (PCP)IrH(tert-butylvinyl) have been observed as the resting states; the ratio of these two complexes is found to be proportional to [TBE]2. Based upon the proportionality constant thus obtained and the catalytic rate as a function of [TBE] (which reaches a maximum at ca. 0.3 M), the respective rate constants for the hydrogenation and dehydrogenation segments can be obtained. Good agreement is found between the rates independently obtained from stoichiometric and catalytic runs. Within the overall TBE-hydrogenation reaction, labeling experiments indicate that the rate-determining step is the reductive elimination of TBA (2,2-dimethylbutane) from (PCP)IrH(tert-butylethyl) (which is formed via insertion of TBE into an Ir-H bond of (PCP)IrH2). Based upon considerations of microscopic reversibility, it can be further inferred that the rate-determining step for the alkane dehydrogenations is C-H addition (and not beta-H elimination).

  DOI：

  10.1021/ja0289200

文献信息

• Cleavage of sp³ C−O Bonds via Oxidative Addition of C−H Bonds
  作者：Jongwook Choi、Yuriy Choliy、Xiawei Zhang、Thomas J. Emge、Karsten Krogh-Jespersen、Alan S. Goldman

  DOI：10.1021/ja906930u

  日期：2009.11.4

  pathway for this reaction that proceeds through C-H addition of the ethoxy methyl group followed by beta-aryl oxide elimination and loss of ethylene. Thus, both of these distinct C-O cleavage reactions proceed via initial addition of a C(sp(3))-H bond, despite the fact that such bonds are typically considered inert and are much stronger than C-O bonds.

  (PCP)Ir (PCP = kappa(3)-C(6)H(3)-2,6-[CH(2)P(t-Bu)(2)](2)) 被发现进行氧化加成缺电子甲基芳基醚（包括甲氧基-3,5-双（三氟甲基）苯和甲氧基五氟苯）的甲基-氧键，得到相应的芳基氧化物配合物（PCP）Ir（CH（3））（OAr）。尽管净反应是将 Ir 中心插入到 CO 键中，但密度泛函理论 (DFT) 计算和显着的动力学同位素效应 [k(CH(3))(OAr)/k(CD(3))(OAr) = 4.3(3)] 强烈反对简单的插入机制，并支持涉及 CH 加成和 OAr 基团的 α 迁移以产生亚甲基复合物，然后氢化物到亚甲基迁移以产生观察到的产物的途径。乙氧基芳基醚，包括乙氧基苯，也会通过 (PCP)Ir 进行 CO 键断裂，但在这种情况下，净反应是 1,2-消除 ArO-H，得到 (PCP)Ir(H)(OAr) 和乙烯。DFT 计算表明该反应的低阻障途径通过乙氧基甲基的
• Addition of C−H Bonds to the Catalytically Active Complex (PCP)Ir (PCP = η³-2,6-(<i>^t</i>Bu₂PCH₂)₂C₆H₃)
  作者：Mira Kanzelberger、Bharat Singh、Margaret Czerw、Karsten Krogh-Jespersen、Alan S. Goldman

  DOI：10.1021/ja001626s

  日期：2000.11.1