[3-Di(propan-2-yl)phosphanyloxy-5-methoxyphenoxy]-di(propan-2-yl)phosphane | 1394791-92-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: [3-Di(propan-2-yl)phosphanyloxy-5-methoxyphenoxy]-di(propan-2-yl)phosphane
• CAS: 1394791-92-4
• 化学式: C₁₉H₃₄O₃P₂
• 分子量: 372.425
• InChiKey: BPIOSCCUWMHLJZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  24
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  [3-Di(propan-2-yl)phosphanyloxy-5-methoxyphenoxy]-di(propan-2-yl)phosphane 以 四氢呋喃 、 氘代四氢呋喃 、 二乙二醇二甲醚 为溶剂， 反应 48.0h， 生成
  参考文献：
  名称：

  Mechanistic Studies of Ammonia Borane Dehydrogenation Catalyzed by Iron Pincer Complexes

  摘要：

  A series of iron bis(phosphinite) pincer complexes with the formula of [2,6-((Pr2PO)-Pr-i)(2)C6H3]Fe-(PMe2R)(2)H (R = Me, 1; R = Ph, 2) or [2,6-((Pr2PO)-Pr-i)(2)-4(MeO)C6H2]Fe(PMe2Ph)(2)H (3) have been tested for catalytic dehydrogenation of ammonia borane (AB). At 60 degrees C, complexes 1-3 release 2.3-2.5 equiv of H-2 per AB in 24 h. Among the three iron catalysts, 3 exhibits the highest activity in terms of both the rate and the extent of H-2 release. The initial rate for the dehydrogenation of AB catalyzed by 3 is first order in 3 and zero order in AB. The kinetic isotope effect (KIE) observed for doubly labeled AB (k(NH3BH3)/k(ND3BD3) = 3.7) is the product of individual KLEs (k(NH3BH3)/k(ND3BH3) = 2.0 and k(NH3BH3)/k(NH3BD3) = 1.7), suggesting that B-H and N-H bonds are simultaneously broken during the rate-determining step. NMR studies support that the catalytically active species is an AB-bound iron complex formed by displacing trans PMe3 or PMe2Ph (relative to the hydride) by AB. Loss of NH3 from the AB-bound iron species as well as catalyst degradation contributes to the decreased rate of H-2 release at the late stage of the dehydrogenation reaction.

  DOI：

  10.1021/ja5058423
• 作为产物：
  描述：

  夫拉美诺 、 氯二异丙基膦 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 生成 [3-Di(propan-2-yl)phosphanyloxy-5-methoxyphenoxy]-di(propan-2-yl)phosphane
  参考文献：
  名称：

  镍的POCOP型钳式配合物：新型阳离子乙腈加合物的合成，表征和配体交换反应性。

  摘要：

  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.

  DOI：

  10.1021/acs.organomet.5b00272

文献信息

• Cobalt POCOP Pincer Complexes via Ligand C–H Bond Activation with Co₂(CO)₈: Catalytic Activity for Hydrosilylation of Aldehydes in an Open vs a Closed System
  作者：Yingze Li、Jeanette A. Krause、Hairong Guan

  DOI：10.1021/acs.organomet.8b00273

  日期：2018.7.9

  A series of cobalt POCOP pincer complexes with the formulas 2,6-(iPr2PO)2-4-R′-C6H2}Co(CO)2 (R′ = H (1a), NMe2 (1b), OMe (1c), CO2Me (1d)), 2,6-(Ph2PO)2C6H3}Co(CO)2 (1e), and 2,6-(tBu2PO)2C6H3}Co(CO) (2f) have been synthesized through C–H bond activation of the corresponding pincer ligands with Co2(CO)8. These complexes have been demonstrated to catalyze the hydrosilylation of PhCHO with (EtO)3SiH

  一系列具有式2,6-（i Pr 2 PO）2 -4-R'-C 6 H 2 } Co（CO）2（R'= H（1a），NMe 2（1b），OMe（1c），CO 2 Me（1d）），2,6-（Ph 2 PO）2 C 6 H 3 } Co（CO）2（1e）和2,6-（t Bu 2 PO）2 C 6 H 3 } Co（CO）（2f）是通过Co 2（CO）8相应的钳形配体的C–H键活化而合成的。这些配合物已被证明可以催化PhCHO与（EtO）3 SiH的氢化硅烷化反应，该反应具有诱导期和递减顺序，依次为1b > 1c > 1a > 1d > 1e。该催化规程可以应用于周转数高达300的各种醛。二羰基络合物中的CO配体在室温下可与13 CO交换，并在高温下与钴部分解离。CO的取代由叔丁基异氰化物在50-80°C时用1a完成，导致形成2,6-（i Pr 2 PO）2 C 6 H 3 } Co（CN
• Nickelation of PCP- and POCOP-Type Pincer Ligands: Kinetics and Mechanism
  作者：Boris Vabre、Melinda L. Lambert、Alban Petit、Daniel H. Ess、Davit Zargarian

  DOI：10.1021/om3003784

  日期：2012.9.10

  This report describes the results of a combined experimental and computational investigation on the kinetics and mechanism of the C–H metalation step involved in the formation of PCP- and POCOP-type complexes of nickel. The kinetics of the C–H nickelation reaction was probed through competition studies involving two ligands reacting with a substoicheometric quantity of (i-PrCN)NiBr2}n. These experiments

  该报告描述了涉及镍的PCP型和POCOP型配合物形成的C–H金属化步骤的动力学和机理的组合实验和计算研究的结果。通过竞争研究探讨了CH镍化反应的动力学，该研究涉及两个配体与亚化学计量的（i- PrCN）NiBr 2 } n反应。这些实验已经证实，与芳族配体1,3-（i -Pr 2 PECH 2）2相比，芳族配体1,3-（i -Pr 2 PE）2 C 6 H 4的金属化更容易。CH 2（SP 2 CH> SP 3 CH; E = O，CH 2），配体轴承膦部分VS那些具有亚膦酸酯基团（PCP> POCOP），配体轴承P取代基我-Pr 2 P VS吨-卜2 P和博士2 P，和POC SP 2 OP配体1,3-（我-Pr 2 PO）2 C ^ 6 - [R ñ ħ 4- ñ轴承供电子VS吸电子取代基（p -OMe≈米- OMe> p -Me> m-CO 2 Me> p -CO 2 Me> m，m
• Thermally Robust and Highly Active PCP Cobalt(II) Catalyst for Linear-Selective Hydroboration of Terminal and Internal Olefins
  作者：Juntao Liu、Jiayan Du、Feng Yu、Lan Gan、Guixia Liu、Zheng Huang

  DOI：10.1021/acscatal.3c01412

  日期：2023.6.16

  (HBpin), furnishing anti-Markovnikov addition products. We also show that linear-selective hydroboration occurs with internal acyclic olefins at elevated temperatures, including those conjugated with the arene or carbonyl groups that are difficult to be achieved by previous catalysts. Such a catalytic property makes this cobalt catalyst suitable for terminally selective formal borylation of arylalkane

  我们报道了在考虑催化剂稳定性的指导下，用于烯烃硼氢化的L 2 X型配体的钴配合物的设计和合成。在 PCP 连接的 Co(II) 和 Co(III) 钳状配合物系列中，具有i 的配合物Pr 膦基取代基在末端烯烃与频那醇硼烷 (HBpin) 的硼氢化反应中，在 ppm 催化剂负载量（17 ppm，0.001 mol%）下表现出广泛的范围、高官能团耐受性和高催化活性，提供反马可夫尼科夫加成产物。我们还表明，在高温下，内无环烯烃会发生线性选择性硼氢化反应，包括那些与芳烃或羰基共轭的烯烃，这是以前的催化剂难以实现的。这种催化特性使得这种钴催化剂适合通过脱氢-硼氢化序列对芳基烷烃进行末端选择性形式硼化。实验机理数据为 Co(II) 氢化物中间体的参与提供了证据。
• 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.