[Ni(κP,κC,κP-2,6-(i-Pr2PO)2C6H3)(NCMe)][OSO2CF3] | 948311-83-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: [Ni(κP,κC,κP-2,6-(i-Pr2PO)2C6H3)(NCMe)][OSO2CF3]
• 英文别名: [(2,6-(i-Pr2PO)2C6H3)Ni(NCCH3)](OTf)；[Ni(POCOP)(NCMe)][OTf]
• CAS: 948311-83-9
• 化学式: CF₃O₃S*C₂₀H₃₄NNiO₂P₂
• 分子量: 590.203
• InChiKey: OKHPULQRTJFDED-UHFFFAOYSA-M

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：

  [Ni(κP,κC,κP-2,6-(i-Pr2PO)2C6H3)(NCMe)][OSO2CF3] 以 氘代苯 为溶剂， 生成 [(2,6-((i-Pr)2PO)2C6H3)NiBr]
  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：

  [(2,6-((i-Pr)2PO)2C6H3)NiBr] 以 氘代苯 为溶剂， 生成 [Ni(κP,κC,κP-2,6-(i-Pr2PO)2C6H3)(NCMe)][OSO2CF3]
  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

• Addition of amines and phenols to acrylonitrile derivatives catalyzed by the POCOP-type pincer complex [{κP,κC,κP-2,6-(i-Pr2PO)2C6H3}Ni(NCMe)][OSO2CF3]
  作者：Xavier Lefèvre、Guillaume Durieux、Stéphanie Lesturgez、Davit Zargarian

  DOI：10.1016/j.molcata.2010.11.010

  日期：2011.2

  anti-Markovnikov addition of nucleophiles to activated olefins. The catalyzed additions of aliphatic amines to acrylonitrile, methacrylonitrile, and crotonitrile proceed at room temperature and give quantitative yields of products resulting from the formation of C–N bonds. On the other hand, aromatic amines or alcohols are completely inert toward methacrylonitrile and crotonitrile, and much less reactive

  钳型配合物[κ P，κ Ç，κ P -2,6-（我-Pr 2 PO）2 C ^ 6 ħ 3 }的Ni（NCMe）] [OSO 2 CF 3 ]（1）可以用作亲核试剂向活性烯烃的区域选择性，反马尔科夫尼科夫加成的前催化剂。脂肪胺在丙烯腈，甲基丙烯腈和巴豆腈中的催化加成反应在室温下进行，并由于形成了C–N键而产生定量的产物收率。另一方面，芳族胺或醇对甲基丙烯腈和巴豆腈是完全惰性的，对丙烯腈的反应性小得多，需要添加碱，加热和延长的反应时间才能获得良好的收率。1的催化反应性据认为是由于配位乙腈的取代不稳定性所致，该取代基使得烯烃底物中腈部分具有竞争性配位；这种结合增强了CC部分的亲电子性，使它们更易于受到亲核试剂的攻击。在某些情况下，RCN→Ni结合会导致双键异构化/迁移（烯丙基氰化物）或亲核体在腈部分（肉桂腈和4-氰基苯乙烯）的侵蚀。吗啉与1在60°C下反应导致形成formation衍生物2，该X衍生物2已通过X射线晶体学表征。
• A Robust Nickel Catalyst for Cyanomethylation of Aldehydes: Activation of Acetonitrile under Base-Free Conditions
  作者：Sumit Chakraborty、Yogi J. Patel、Jeanette A. Krause、Hairong Guan

  DOI：10.1002/anie.201302613

  日期：2013.7.15

  room temperature coupling of aldehydes with acetonitrile under base‐free conditions. The catalytic system is long‐lived and remarkably efficient with high turnover numbers (TONs) and turnover frequencies (TOFs) achieved. The mild reaction conditions allow a wide variety of aldehydes, including base‐sensitive ones, to catalytically react with acetonitrile.

  时间的缺口：氰基甲基镍镍络合物1在无碱条件下催化醛与乙腈的室温偶联。该催化系统寿命长且效率高，可实现高周转率（TON）和周转率（TOF）。温和的反应条件使各种醛（包括碱敏感的醛）与乙腈发生催化反应。
• New Pincer-Type Diphosphinito (POCOP) Complexes of Nickel
  作者：Valerica Pandarus、Davit Zargarian

  DOI：10.1021/om700400x

  日期：2007.8.1

  paramagnetic, 17-electron species (i-Pr2POCH2)2CH}NiIIIX2 (X = Cl, 2i; Br, 2j). Solid-state structures are reported for Ni−halide derivatives, the neutral complexes 2d, 1g, and 1h, the cationic adduct 1e, and the Ni(III) derivative 2i. The cationic acrylonitrile derivative 1f promotes the Michael addition of morpholine, cyclohexyl amine, or aniline to acrylonitrile, methacrylonitrile, or crotonitrile

  本报告描述了合成，表征，以及基于所述diphosphinito一系列新的钳型镍配合物的反应性的（POCOP）配体1,3-（异镨2 PO）2 C ^ 6 ħ 4，1，和（我-Pr 2 POCH 2）2 CH 2，2。这些配体与（THF）1.5 NiCl 2，（THF）2 NiBr 2或（CH 3 CN）n NiX 2（X = Br，n = 2; I，n＝ 3）通过中心碳原子的金属化得到钳型配合物。这些（POCOP）NiX配合物的产率随所用配体和Ni前驱体的类型以及反应条件而变化。通常，芳族配体1更易于金属化，从而获得极佳的钳形配合物2,6-（i- Pr 2 PO）2 C 6 H 3 } NiX（X = Cl，1a，85％产率; X ＝ Br，1b，95％收率； X ＝ I，1c，85％收率），特别是当在1当量的4-二甲基氨基吡啶（DMAP）存在下将反应混合物加热至60℃达1小时时。配体2的
• New POCOP-type pincer complexes of Nickel(II)
  作者：Xavier Lefèvre、Denis M. Spasyuk、Davit Zargarian

  DOI：10.1016/j.jorganchem.2010.10.019

  日期：2011.2

  The pincer complex [(POCOP)Ni(NCMe)][OSO2CF3] (1: POCOP = (2,6-i-Pr2PO)(2)C6H3}) undergoes an acetonitrile substitution reaction in the presence of CN(t-Bu), KCN, and KOCN to give the new complexes [(POCOP)NiCN(t-Bu)}][O3SCF3]and (POCOP)Ni(X) (X=CN and NCO). The Ni CN derivative is also obtained from a gradual decomposition of the Ni CN(t-Bu) derivative, while the aquo derivative [(POCOP)Ni(OH2)] [O3SCF3] was obtained from slow hydrolysis of (POCOP)Ni(OSO2CF3). All new complexes have been characterized spectroscopically and by X-ray crystallography. IR and solid state structural data indicate that Ni-L/X interactions are dominated by ligand-to-metal sigma-donation; presence of little or no pi-backbonding is consistent with the electrophilicity of the cationic fragment [(POCOP)Ni](+). (C) 2010 Elsevier B.V. All rights reserved.