(2,6-C6H3(CH2P(t-Bu)2)2)IrH(Ph) | 312960-70-6

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: (2,6-C6H3(CH2P(t-Bu)2)2)IrH(Ph)
• 英文别名: (κ3-C6H3-2,6-(CH2P(t)Bu2)2)IrPhH；(PCP)IrPhH；(PCP)IrH(Ph)
• CAS: 312960-70-6
• 化学式: C₃₀H₄₉IrP₂
• 分子量: 663.887
• InChiKey: VGVXEKBKYNODJU-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：

  (2,6-C6H3(CH2P(t-Bu)2)2)IrH(Ph) 以 苯 为溶剂， 生成 (κ3-C6H3-2,6-(CH2P(t)Bu2)2)Ir(PhC=CH2)(C2Ph)
  参考文献：
  名称：

  Dimerization of Alkynes Promoted by a Pincer-Ligated Iridium Complex. C−C Reductive Elimination Inhibited by Steric Crowding

  摘要：

  The pincer-ligated species (PCP)Ir (PCP = kappa(3)-C6H3-2,6-((CH2PBu2)-Bu-t)(2)) is found to promote dimerization of phenylacetylene to give the enyne complex (PCP)Ir(trans-1,4-phenyl-but-3-ene-1-yne). The mechanism of this reaction is found to proceed through three steps: (i) addition of the alkynyl C-H bond to iridium, (ii) insertion of a second phenylacetylene molecule into the resulting Ir-H bond, and (iii) vinyl-acetylide reductive elimination. Each of these steps has been investigated, by both experimental and computational (DFT) methods, to yield unexpected conclusions of general interest. (i) The product of alkynyl C-H addition, (PCP)Ir(CCPh)(H) (3), has been isolated and, in accord with experimental observations, is calculated to be 29 kcal/mol more stable than the analogous product of benzene C-H addition. (ii) Insertion of a second PhCCH molecule into the Ir-H bond of 3 proceeds rapidly, but with a 1,2-orientation. This orientation gives (PCP)Ir(CCPh)(CPhCH2) (4) which would yield the 1,3-diphenyl-enyne if it were to undergo C-C elimination; however, the insertion is reversible, which represents the first example, to our knowledge, of simple beta-H elimination from a vinyl group to give a terminal hydride. The 2,1-insertion product (PCP)Ir(CCPh)(CHCHPh) (6) forms more slowly, but unlike the 1,2 insertion product it undergoes C-C elimination to give the observed enyne. (iii) The failure of 4 to undergo C-C elimination is found to be general for (PCP)Ir(CCPh)(vinyl) complexes in which the vinyl group has an alpha-substituent. Thus, although C-C elimination relieves crowding, the reaction is inhibited by increased crowding. Density-functional theory (DFT) calculations support this surprising conclusion and offer a clear explanation. Alkynyl-vinyl bond formation in the C-C elimination transition state involves the vinyl group pi-system; this requires that the vinyl group must rotate (around the Ir-C bond) by ca. 90 degrees to achieve an appropriate orientation. This rotation is severely inhibited by steric crowding, particularly when the vinyl group bears an alpha-substituent.

  DOI：

  10.1021/ja0647194
• 作为产物：
  描述：

  苯 、 [(1,3-bis((di-tert-butylphosphino)methyl)benzene(-1H))IrH2] 在 tert-butylethene or norbornene 作用下， 以 苯 为溶剂， 生成 (2,6-C6H3(CH2P(t-Bu)2)2)IrH(Ph)
  参考文献：
  名称：

  向催化活性配合物 (PCP)Ir 添加 C-H 键 (PCP = η3-2,6-(tBu2PCH2)2C6H3)

  摘要：

  DOI：

  10.1021/ja001626s

文献信息

• N−H Activation of Hydrazines by Iridium(I). Double N−H Activation To Form Iridium Aminonitrene Complexes
  作者：Zheng Huang、Jianrong (Steve) Zhou、John F. Hartwig

  DOI：10.1021/ja1053835

  日期：2010.8.25

  1-aminopiperidine to iridium(I) complexes give the corresponding hydridoiridium(III) hydrazido complexes within minutes. The complex containing an aromatic pincer ligand, (PCP)Ir(H)(NHNC(5)H(10)), slowly undergoes a second N-H bond cleavage at the alpha-N-H bond and elimination of hydrogen to generate an aminonitrene complex and dihydrogen in high yield. The reactions of the (PCP)Ir(I) fragment containing

  芳香族 (PCP) 和脂肪族 (D(t)BPP) 钳形配体的铱 (I) 配合物对肼衍生物的 NH 键进行单裂解以形成肼基配合物，并通过成对双裂解形成不寻常的晚期过渡金属氨基氮化合物。在某些情况下，还观察到肼中 NN 键的断裂。二苯甲酮腙和 1-氨基哌啶的 NH 键氧化加成到铱 (I) 络合物，在几分钟内得到相应的氢化铱 (III) 肼基络合物。含有芳香钳状配体 (PCP)Ir(H)(NHNC(5)H(10)) 的复合物在 α-NH 键处缓慢发生第二次 NH 键断裂并消除氢以生成氨基氮化合物和二氢高产。(PCP)Ir(I) 片段含有芳香钳位配体与甲基取代的肼反应形成氨基氮化合物、异氰化铱 (III) 二氢化物配合物和氨的混合物。后两种产物可能是由甲基 CH 键的初始氧化加成和随后的 NN 键断裂形成的。氨基氮化合物与 CO 或进行氧化加成的试剂（MeI 和 PhOH）的反应导致“异二嗪”片段的释放，得到四氮烯和四嗪衍生物。
• Reactions of iridium hydride pincer complexes with dioxygen: new dioxygen complexes and reversible O2 binding
  作者：D. Bridget Williams、Werner Kaminsky、James M. Mayer、Karen I. Goldberg

  DOI：10.1039/b802739k

  日期：——

  The reaction of molecular oxygen with iridium pincer hydride complexes, ((tBu)PCP)Ir(H)(X) [(tBu)PCP = kappa(3)-C(6)H(3)(CH(2)P(t)Bu(2))(2), X = Ph, H, CCPh], results in O(2) induced reductive elimination and formation of the novel dioxygen complexes ((tBu)PCP)Ir(O(2))(n) [n = 1 (), 2 ()].

  分子氧与氢化铱铱络合物（（（tBu）PCP）Ir（H）（X）[（tBu）PCP = kappa（3）-C（6）H（3）（CH（2）P（ t）Bu（2））（2），X = Ph，H，CCPh]，导致O（2）诱导的还原消除和新型双氧配合物（（tBu）PCP）Ir（O（2））（ n）[n = 1（），2（）]。
• Mechanism of Alkane Transfer-Dehydrogenation Catalyzed by a Pincer-Ligated Iridium Complex
  作者：Kenton B. Renkema、Yury V. Kissin、Alan S. Goldman

  DOI：10.1021/ja0289200

  日期：2003.7.1

  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).