[(2,6-((i-Pr)2PO)2C6H3)NiBr] | 934482-00-5

• 英文名称: [(2,6-((i-Pr)2PO)2C6H3)NiBr]
• 英文别名: [(2,6-(iPr2PO)2C6H3-κ3C,P,P')NiBr]
• CAS: 934482-00-5
• 化学式: C₁₈H₃₁BrNiO₂P₂
• 分子量: 479.984
• InChiKey: IQQLYXCCUFKSQW-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：

  [(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
• 作为产物：
  描述：

  以 乙腈 为溶剂， 生成 [(2,6-((i-Pr)2PO)2C6H3)NiBr]
  参考文献：
  名称：

  基于POCN型和POCOP型钳型配体的镍阳离子四和五配位配合物：合成，表征和配体交换研究

  摘要：

  搅拌乙腈电荷中性钳形络合物的溶液（POCN）NIBR（1，POCN =κ P，κ Ç，κ ñ - {2-（I-PR）2 PO，6-CH 2 {CN（CH 2）5 } -C 6 ħ 3）和（POCOP）NIBR（2，POCOP =κ P，κ ç，κ P' -2,6-（I-PR 2 OP）2 C ^ 6 ħ 3）与AgSbF 6功能有助于溴-提取得到相应的阳离子乙腈加合物[（POCN）Ni（NCMe）] +，1a和[（POCOP）Ni（NCMe）] +，2a。用吡啶（py），2,2'-联吡啶（bipy），菲咯啉（phen）或4,4'-联吡啶（bipy *）处理1a和2a得到相应的单阳离子加合物[（POCN或POCOP）Ni（配体）] +（配体= PY：图1b和2b中;κ ñ，κ N' -bipy：1C和2C ;κ ñ，κ N' -苯：1D和2D）和双阳离子双核加合物[（POCN或POCOP）2

  DOI：

  10.1039/d1nj01355f

文献信息

• 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
• 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
• New pincer-type diphosphinito (POCOP) complexes of Ni^IIand Ni^III
  作者：Valerica Pandarus、Davit Zargarian

  DOI：10.1039/b613812h

  日期：——

  This communication reports the synthesis and characterization of the new, pincer-type, square-planar, 16-electron compounds 2,6-(OPPri2)2C6H3}NiIIBr, 1, and (Pri2POCH2)2CH}NiIIBr, 2, and the square-pyramidal, 17-electron complex (Pri2POCH2)2CH}NiIIIBr2, 3.

  这篇通讯报道了新型钳形、方形平面、16 电子化合物 2,6-(OPPri2)2C6H3}NiIIBr, 1 和 (Pri2POCH2)2CH}NiIIBr, 2 以及方形金字塔、17 电子复合物 (Pri2POCH2)2CH}NiIIIBr2, 3 的合成和表征。
• Substituent effects on Ni–S bond dissociation energies and kinetic stability of nickel arylthiolate complexes supported by a bis(phosphinite)-based pincer ligand
  作者：Jie Zhang、Anubendu Adhikary、Krista M. King、Jeanette A. Krause、Hairong Guan

  DOI：10.1039/c2dt30407d

  日期：——

  Pincer complexes of the type [2,6-(R2PO)2C6H3]NiSC6H4Z (R = Ph and i-Pr; Z = p-OCH3, p-CH3, H, p-Cl, and p-CF3) have been synthesized from [2,6-(R2PO)2C6H3]NiCl and sodium arylthiolate. X-ray structure determinations of these thiolate complexes have shown a somewhat constant Ni–S bond length (approx. 2.20 Å) but an almost unpredictable orientation of the thiolate ligand. Equilibrium constants for various thiolate exchange (between a nickel thiolate complex and a free thiol, or between two different nickel thiolate complexes) reactions have been measured. Evidently, the thiolate ligand with an electron-withdrawing substituent prefers to bond with “[2,6-(Ph2PO)2C6H3]Ni” rather than “[2,6-(i-Pr2PO)2C6H3]Ni”, and bonds least favourably with hydrogen. The reactions of the thiolate complexes with halogenated compounds such as PhCH2Br, CH3I, CCl4, and Ph3CCl have been examined and several mechanistic pathways have been explored.

  [2,6-(R2PO)2C6H3]NiSC6H4Z 型钳配合物（R = Ph 和 i-Pr；Z = p-O 、p-CH3、H、p-Cl 和 p-CF3）已由[2,6-(R2PO)2C6H3]NiCl和芳基硫醇钠。这些硫醇盐配合物的 X 射线结构测定显示 Ni-S 键长有些恒定（约 2.20 ×），但硫醇盐配体的方向几乎不可预测。测量了各种硫醇盐交换（硫醇镍络合物和游离硫醇之间，或两种不同的硫醇镍络合物之间）反应的平衡常数。显然，具有吸电子取代基的硫醇盐配体更喜欢与 -[2,6-(Ph2PO)2C6H3]Ni-而不是 -[2,6-(i-Pr2PO)2C6H3]Ni-键合，并且与氢的键合最不利。硫醇盐配合物与卤代化合物（例如 PhCH2Br、 I、CCl4 和 Ph3CCl）的反应已得到检验，并探索了几种机理途径。
• Regioselective Hydroamination of Acrylonitrile Catalyzed by Cationic Pincer Complexes of Nickel(II)
  作者：Annie Castonguay、Denis M. Spasyuk、Nathalie Madern、André L. Beauchamp、Davit Zargarian

  DOI：10.1021/om800840u

  日期：2009.4.13

  characterized by NMR spectroscopy and X-ray crystallography. Cyclic voltammetry measurements of the Ni−Br precursors of 2, 3, and 6 indicated that substituting the CH2 moiety in the ligand skeleton by O, or some of the aromatic protons by Cl, renders the metal center less susceptible to oxidation. Evaluating the catalytic activities of 1−3, 6, and the t-Bu analogue of 1 for addition of aniline to acrylonitrile

  阳离子钳型配合物[（i -Pr 2 PCH 2 CH 2）2 CH} Ni（NCCH 3）] [BPh 4 ]（1），[2,6-（i -Pr 2 PCH 2）2 -C 6 H 3 } Ni（NCCH 3）] [BPh 4 ]（2），[2,6-（i -Pr 2 PO）2 -C 6 H 3 } Ni（NCCH 3）] [BPh 4 ] （3）和[2,6-（i已经制备了-Pr 2 PO）2 -3，5-Cl 2 -C 6 H} Ni（NCCH 3）] [BPh 4 ]（6），并通过NMR光谱和X射线晶体学对其进行了充分表征。的镍-溴前体的循环伏安法的测量2，3，和6表示取代CH 2被O在配体骨架部分，或一些经Cl的芳族质子的，使得该金属中心不易被氧化。评估的催化活性1 - 3，6，和吨的-Bu类似物1将苯胺加到丙烯腈中的结果表明3是最有效的催化剂前体。的分离[（吨-Bu 2 PCH 2 CH