| 1073856-67-3

• CAS: 1073856-67-3
• 化学式: C₁₇H₃₇BrNiP₂
• 分子量: 442.022
• InChiKey: GPRARHNYQGRHCI-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：

  以 氘代苯 为溶剂， 生成 [((i-Pr2PCH2CH2)2CH)Ni(H2O)][BF4]
  参考文献：
  名称：

  New Derivatives of PCP-Type Pincer Complexes of Nickel

  摘要：

  The pincer-type complexes (PCsp3Pi-Pr)NiR (PCsp3Pi-Pr = (i-Pr2PCH2CH2)(2)CH) react with HBF4 (R = C equivalent to CMe, Ph, Me) or AgBF4 (R = Br) to give (PCsp3 Pi-Pr)Ni(BF4), 1, which was found to involve fluxional Ni-F-BF3 interactions. Competition experiments revealed that the relative ease of protonation of the Ni-hydrocarbyl moiety follows the order Ni-Me > Ni-C equivalent to CMe > Ni-Ph. Complex 1 reacts with water to give [(PCsp3Pi-Pr)Ni(H2O)][BF4], 2, that in turn undergoes H2O exchange with CH3CN, i-PrNH2, and CO to give the corresponding cationic adducts 3, 4, and 5; alternatively, 3-5 can also be obtained directly from the reaction of 1 with CH3CN, i-PrNH2, and CO, respectively. Deprotonation of complex 2 gives the neutral hydroxo complex (PCsp3Pi-Pr)Ni(OH), 6. All complexes have been characterized by NMR spectroscopy and, in the case of 2-6, by X-ray crystallography.

  DOI：

  10.1021/ic801641u
• 作为产物：
  描述：

  在 4-Me₂NC₅H₄N 作用下， 以 甲苯 为溶剂， 生成
  参考文献：
  名称：

  Preparation and Reactivities of PCP-Type Pincer Complexes of Nickel. Impact of Different Ligand Skeletons and Phosphine Substituents

  摘要：

  Reaction of the diphosphine ligand i-Pr2P(CH2)(5)P(i-Pr)(2) with NiBr2 at 110 degrees C gives a mixture of the 16-membered bimetallacycle {i-Pr2(P)(CH2)SP(i-Pr)(2)}(2)Ni2Br4, 1, and the pincer-type complex {(i-Pr2PCH2CH2)(2)CH}NiBr, 2; the latter can also be obtained by heating 1 in the presence of 4-(dimethylamino)pyridine or under vacuum. Complex 2 undergoes transmetalation with RMgCl or RLi to give {(i-Pr2PCH2CH2)(2)CH}NiR (R = Me (4), C CMe (5), Ph (6), n-Bu (7), and C CPh (8)); the phenylacetylide derivative 8 was also obtained from the reaction of PhC CH with 4, 5, or 7. The Ni-Me derivative 4 reacts with PhX (X = I, Br, Cl) to give the product of C-C coupling reaction (Ph-Me) and the Ni-X analogues of 2, and tests have shown that 2 is a competent catalytic precursor for the coupling of PhCl and MeMgCl. The available evidence suggests that this catalytic process does not involve Ni intermediates. Indeed, cyclic voltammetry measurements show that 2 can undergo two consecutive oxidations, and attempts to generate isolable high-valent species yielded the five-coordinate, 17-electron Ni-III species {(i-Pr2PCH2CH2)(2)CH}NiX2, 9, from the reaction of 2 with FeX3 (X = Cl, Br). Characterization of all new complexes, including X-ray diffraction studies on single crystals of complexes 1-6 and 9, is described.

  DOI：

  10.1021/om8005454

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
• 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
• POCOP-Type Pincer Complexes of Nickel: Synthesis, Characterization, and Ligand Exchange Reactivities of New Cationic Acetonitrile Adducts
  作者：Sébastien Lapointe、Boris Vabre、Davit Zargarian

  DOI：10.1021/acs.organomet.5b00272

  日期：2015.7.27

  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.