4,6-di-tert-butylresorcinolbis(diisopropylphosphinite) | 886987-21-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4,6-di-tert-butylresorcinolbis(diisopropylphosphinite)
• 英文别名: [2,4-Ditert-butyl-5-di(propan-2-yl)phosphanyloxyphenoxy]-di(propan-2-yl)phosphane
• CAS: 886987-21-9
• 化学式: C₂₆H₄₈O₂P₂
• 分子量: 454.613
• InChiKey: IKYIRVHYGLUAQJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.2
• 重原子数：
  30
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,6-di-tert-butylresorcinolbis(diisopropylphosphinite) 在 sodium t-butanolate 作用下， 以 甲苯 为溶剂， 反应 4.33h， 生成 (^tBuPOCOP)Rh(CHCH₂)(OTf)
  参考文献：
  名称：

  钳夹式Rh（III）和主要副反应的潜在碳-氟还原消除反应：理论和实验检查

  摘要：

  本文探讨了从Rh（III）夹杂物络合物中CF还原消除的潜力。甲DFT计算研究表明从（POCOP）的Rh（CHCH采取一致C-F还原消除2）（F）（3）（其中POCOP是κ 3 P，Ç，P -2,6（我镨2 PO）2 Ç 6 ħ 3，和芳基/双（膦酸酯）钳形配体）具有Δ的实验似是而非活化能垒ģ ⧧ = 28.3千卡/摩尔。该势垒大大低于从（POCOP）Rh（Ph）（F）中类似的CF还原消除计算得出的势垒（35.7 kcal / mol）（1）。差异归因于在过渡状态下苯基或乙烯基的部分旋转的需要，其中苯基更受支撑钳式配体的空间体积的束缚。DFT计算并未分析可能的副反应的全部范围，事实已证明是主要的。的尝试的合成1是不成功的，因为在（POCOP）铑的准备阶段竞争C-C的还原消除反应（CHCH 2）（I）前体。DFT计算预测，由于产品固有的应变，在单体单元中进行C–C还原消除很容易，但明显不利。该

  DOI：

  10.1021/om5008902
• 作为产物：
  描述：

  氯二异丙基膦 、 4,6-二叔丁基间苯二酚 在 三乙胺 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以46%的产率得到4,6-di-tert-butylresorcinolbis(diisopropylphosphinite)
  参考文献：
  名称：

  铱的POCOP型钳形配合物催化的高转化率芳烃C-H硼化

  摘要：

  已经证明了使用 Ir 的 POCOP 型钳形复合物对芳烃与 HBpin（pin = 频哪酸酯）的催化 CH 硼化，在某些情况下转换数超过 10 000。CH 活化的选择性基于空间偏好，并且在很大程度上反映了在其他 Ir 硼化催化剂中发现的选择性。(POCOP)Ir 系统中的催化取决于化学计量数量的牺牲烯烃的存在，该牺牲烯烃被氢化以消耗在 CH 键与 HBpin 的硼酸化中产生的 H2 等价物。较小的烯烃如乙烯或 1-己烯比空间阻碍的叔丁基乙烯 (TBE) 更有利于催化。烯烃硼氢化反应是一种竞争性副反应。可能与催化相关的多种复合物的合成和分离允许检查几个关键的基本反应。这些实验表明，催化中的 CH 活化步骤表面上涉及将芳族 CH 键氧化加成到三配位 (POCOP) Ir 物质上。烯烃对于获得这种 14 电子单价 Ir 中间体在机械上至关重要。此处 Ir(I) 处的 CH 活化与使用由中性双齿配体支持的最先进

  DOI：

  10.1021/jacs.6b03656

文献信息

• Impact of Backbone Substituents on POCOP-Ni Pincer Complexes: A Structural, Spectroscopic, and Electrochemical Study
  作者：Boris Vabre、Denis M. Spasyuk、Davit Zargarian

  DOI：10.1021/om3009475

  日期：2012.12.24

  When treated at room temperature and in the presence of NEt3 with (i-PrCN)NiBr2}(n), the pincer-type ligands R-(POCOPR')-O-H undergo direct C-H nickellation to give the pincer complexes (R-POCOPR')NiBr in 45-92% yields (R-POCOP = kappa(P),kappa(C),kappa(P)-R-n-2,6-(R'2PO)(2)C6H3-n}; R-n = 4-OMe, 4-Me, 4-CO2Me, 3-OMe, 3-CO2Me, 3,5-t-Bu-2; R' = i-Pr, t-Bu). These complexes have been characterized by multinuclear NMR and UV-vis spectroscopy as well as single-crystal X-ray diffraction studies to delineate the impact of R and R' on Ni-ligand interactions. The solid-state structural data have revealed slightly shorter Ni-Br bonds in the complexes bearing a 4-CO2Me substituent, shorter Ni-P bonds in the complex bearing t-Bu substituents at the 3- and 5-positions, and longer Ni-P bonds in complexes featuring OP(t-Bu)(2) donor moieties. The UV-vis spectra indicate that a 4-CO2Me substituent causes a red-shift in the frequency of the MLCT bands (330-365 nm), whereas the ligand field transitions appearing in the 380-420 nm region are influenced primarily by the P-substituents. Cyclic voltammetry measurements have shown that the oxidation potentials of the title complexes are affected by P- and ring-substituents, oxidation being somewhat easier with t-Bu2PO (vs i-Pr2PO), OMe and Me (vs CO2Me), and t-Bu (vs Cl). Moreover, oxidation potentials are affected more by the aromatic substituents at the 4-position vs those at the 3- and 5-positions.
• POCOP-Type Pincer Complexes of Nickel: Synthesis, Characterization, and Ligand Exchange Reactivities of New Cationic Acetonitrile Adducts
  作者：Sébastien Lapointe、Boris Vabre、Davit Zargarian

  DOI：10.1021/acs.organomet.5b00272

  日期：2015.7.27

  This report describes the synthesis, characterization, and ligand exchange studies of a family of cationic acetonitrile adducts of nickel featuring resorcinol-based, pincer-type POCOP ligands. The compounds [(R-POCOPR')Ni(NCMe)][OSO2CF3] (R-POCOPR' = 2,6-(R'2PO)(2)(RnC(6)H(3)n); R' = i-Pr: R = H (1), p-Me (2), p-OMe (3), p-CO2Me (4), p-Br (5), m,m-t-Bu2 (6), m-OMe (7), m-CO2Me (8); R' = t-Bu: R = H (9), p-CO2Me (10)) were prepared in 80-93% yields by reacting the corresponding charge-neutral bromo derivatives with Ag(OSO2CF3) in acetonitrile. The impact of the R- and R'-substituents on electronics and structures of 1-10 have been probed by NMR, UVvis, and IR spectra, X-ray crystallography, and cyclic voltammetry measurements. The observed nu(C=N) values were found to increase with the increasing electron-withdrawing nature of R, i.e., in the order 7 < 3 similar to 2 similar to 6 < 1 < 5 similar to 8 < 4 and 9 < 10. This trend is consistent with the anticipation that enhanced electrophilicity of the nickel center should result in an increase in net MeCN -> Ni sigma-donation. That this transfer of electron density from acetonitrile to the nickel center does not adequately counteract the impact of electron-withdrawing substituents was evident from the measured redox potentials: the MeO2C-substituted cations showed the highest oxidation potentials. Moreover, all cationic adducts showed greater oxidation potentials compared with their corresponding charge-neutral bromo precursors. Equilibrium studies conducted with selected [(R-POCOPR')Ni(NCMe)][OSO2CF3] and (R-POCOPR')NiBr (R' = i-Pr) have confirmed facile MeCN/Br exchange between these derivatives and show that the cationic adducts are stabilized with MeO-POCOP, whereas the charge-neutral bromo species are stabilized with MeO2C-POCOP. The potential implications of these findings for the catalytic reactivities of the title cationic complexes have been discussed.
• Ruthenium PCP–bis(phosphinite) pincer complexes
  作者：Robin B. Bedford、Michael Betham、Michael E. Blake、Simon J. Coles、Sylvia M. Draper、Michael B. Hursthouse、P. Noelle Scully

  DOI：10.1016/j.ica.2005.07.050

  日期：2006.4

  The reactions of [RuHCl(CO)(PPh3)(3)] with resorcinol bis(phosphinite) pincer ligands lead to complexes of the general formula [RuCl(PCP)(CO)(PPh3)]; the crystal structure of one example has been determined. The structures of the bulky resorcinol 2-methyl4,6-di-tert-butyl resorcinol and its mono-diisopropylphosphinite derivative were also determined. Reactions of [RuCl2(PPh3)(3)] with resorcinot bis(phosphinite) ligands yield complexes of the type [RuCl(PCP)(PPh3)], while the reaction of C6H-2-Me-4,6-'Bu-2-1,3-(OPPh2) with [RuHCl(CO)(PPh3)(3)] provides a PCP-pincer complex in which the ligand has undergone 2-methyl C-H activation. (c) 2005 Elsevier B.V. All rights reserved.
• Simple Palladacyclic and Platinacyclic Catalysts for the 1,4-Conjugate Addition of Arylboronic Acids and Arylsiloxanes to Enones
  作者：Robin B. Bedford、Michael Betham、Jonathan P. H. Charmant、Mairi F. Haddow、A. Guy Orpen、Lukasz T. Pilarski、Simon J. Coles、Michael B. Hursthouse

  DOI：10.1021/om700724c

  日期：2007.12.1

  A range of palladacyclic, platinacyclic, and pincer-based catalysts have been tested for activity in 1,4-conjugate addition reactions. pi-Acidic palladacycles show excellent activity at room temperature in the reaction of enones with arylboronic acids and reasonable activity when the arylboronic acids are replaced by arylsiloxanes. The X-ray structures of three new palladium kappa(3)-"PCP"-pincer complexes are presented; surprisingly, these complexes show no activity, despite the fact that notionally related phosphine and carbene adducts of palladacycles do.