Methyl 3,5-bis(ditert-butylphosphanyloxy)benzoate | 1394791-97-9

• 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: Methyl 3,5-bis(ditert-butylphosphanyloxy)benzoate
• CAS: 1394791-97-9
• 化学式: C₂₄H₄₂O₄P₂
• 分子量: 456.543
• InChiKey: ROVMOHVAKFIDLL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  30
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Methyl 3,5-bis(ditert-butylphosphanyloxy)benzoate 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 生成
  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
• 作为产物：
  描述：

  二叔丁基氯化膦 、 3,5-二羟基苯甲酸甲酯 在 sodium hydride 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 反应 2.0h， 生成 Methyl 3,5-bis(ditert-butylphosphanyloxy)benzoate
  参考文献：
  名称：

  双（次膦酸酯）夹钳连接的氯化镍，异硫氰酸盐和叠氮化物络合物的复分解反应性

  摘要：

  [4-Z-2,6-（R 2 PO）2 C 6 H 2 ] NiX（R =  t Bu，i Pr，Ph; Z = H，CO 2 Me; X的一系列镍钳形配合物=  ñ CS，N 3）已经从相应的氯化镍配合物[4-Z-2,6-（R的反应合成2 PO）2 c ^ 6 ħ 2] NiCl和硫氰酸钾或叠氮化钠。对这些配合物的X射线结构测定表明，硫氰酸根离子通过氮与镍中心键合。观察到这些配合物具有可比的Ni–N键长（异硫氰酸酯配合物约为1.87Å，叠氮化物配合物约为1.91Å）和Ni–C ipso键长度（约1.89Å）几乎相同。[4-Z-2,6-（R 2 PO）2 C 6 H 2的复分解反应性已经研究了异硫氰酸镍和叠氮化镍配合物之间的NiCl和配体交换反应。硫氰酸盐/叠氮化物络合物的复分解反应速度更快，电子富集较少，空间中心位置更易接近。这些镍配合物的热力学稳定性已经使用硬-软酸碱理论（HSAB理论）

  DOI：

  10.1016/j.jorganchem.2015.12.038

文献信息

• 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
• 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.
• Iridium Pincer Catalysts for Silane Dehydrocoupling: Ligand Effects on Selectivity and Activity
  作者：Neil T. Mucha、Rory Waterman

  DOI：10.1021/acs.organomet.5b00486

  日期：2015.8.10

  Catalytic reactions of bisphosphinite pincer-ligated iridium compounds p-X-R(POCOP)IrHC1 (POCOP) [2,6-(R2PO)(2)C6H3, R = Pr-i, X = H (1); R = Bu-t, X = COOMe (2); = H (3); = NMe2 (4)] with primary and secondary silanes have been performed. Complex 1 is primarily a silane redistribution precatalyst, but dehydro coupling catalysis is observed for sterically demanding silane substrates or with aggressive removal of H-2. The bulkier compounds (2-4) are silane dehydrocoupling precatalysts that also undergo competitive redistribution with less hindered substrates. Products generated from reactions utilizing 2-4 include low molecular weight oligosilanes with varying degrees of redistribution present or disilanes when employing more sterically demanding silane substrates. Selectivity for redistribution versus dehydrocoupling depends on the steric and electronic environment of the metal but can also be affected by reaction conditions.