Methyl 3,5-bis[di(propan-2-yl)phosphanyloxy]benzoate | 1394791-94-6

• 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[di(propan-2-yl)phosphanyloxy]benzoate
• CAS: 1394791-94-6
• 化学式: C₂₀H₃₄O₄P₂
• 分子量: 400.435
• InChiKey: RCHXUMZDXPAWBK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  26
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.65
• 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[di(propan-2-yl)phosphanyloxy]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：

  氯二异丙基膦 、 3,5-二羟基苯甲酸甲酯 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以89%的产率得到Methyl 3,5-bis[di(propan-2-yl)phosphanyloxy]benzoate
  参考文献：
  名称：

  Impact of Backbone Substituents on POCOP-Ni Pincer Complexes: A Structural, Spectroscopic, and Electrochemical Study

  摘要：

  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.

  DOI：

  10.1021/om3009475

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
• Metathesis reactivity of bis(phosphinite) pincer ligated nickel chloride, isothiocyanate and azide complexes
  作者：Huizhen Li、Wenjuan Meng、Anubendu Adhikary、Shujun Li、Nana Ma、Qianyi Zhao、Qiuyu Yang、Nathan A. Eberhardt、Kendra M. Leahy、Jeanette A. Krause、Jie Zhang、Xuenian Chen、Hairong Guan

  DOI：10.1016/j.jorganchem.2015.12.038

  日期：2016.2

  and ligand exchange reactions between the nickel isothiocyanate and nickel azide complexes have been investigated. The metathesis reactions with thiocyanate/azide complexes are faster with a less electron rich and more sterically accessible nickel center. The thermodynamic stability of these nickel complexes has been rationalized using hard-soft acid-base theory (HSAB theory); a harder ligand prefers

  [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）
• 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