[(2,6-bis(diisopropylphosphinomethyl)phenyl)Ni-Br] | 688009-94-1

• 英文名称: [(2,6-bis(diisopropylphosphinomethyl)phenyl)Ni-Br]
• 英文别名: [(^iPrPCP)Ni-Br]；(2,6-bis(diisopropylphosphinomethyl)phenyl)bromonickel；Ni(2,6-bis((diisopropylphosphino)methyl)phenyl)(Br)；[(2,6-((i-Pr)2PCH2)2C6H3)NiBr]
• CAS: 688009-94-1
• 化学式: C₂₀H₃₅BrNiP₂
• 分子量: 476.039
• InChiKey: RWPNPMAHHFPCGK-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-bis(diisopropylphosphinomethyl)phenyl)Ni-Br] 以 四氢呋喃 为溶剂， 反应 4.0h， 生成 [(2,6-bis(diisopropylphosphino)phenyl)Ni(OEt)]
  参考文献：
  名称：

  具有频繁的脂肪族Alkoxo配体[[ iPr PCP）Ni-OR]的镍钳形配合物（R = Et，n Bu，i Pr，2-羟乙基）。镍和钯醇盐的水解稳定性评估

  摘要：

  一系列具有末端烷氧基配体的镍钳形配合物[（iPr PCP）Ni-OR]（R = Et，n Bu，i Pr，CH 2 CH 2 OH; iPr PCP是2,6-双（二异丙基膦甲基）苯基钳合成并充分表征。这些配合物与先前报道的Ni和Pd的甲氧基类似物一起，构成了一系列独特的等结构后期过渡金属醇盐。光谱和X射线衍射数据提供了其共价Ni-OR键的强极化的直接指示。这类化合物最显着的特征之一是它们易于水解并伴有微量水分，从而与相应的氢氧化物形成平衡混合物[[iPr PCP）M–OH]（M = Ni或Pd）和醇类，ROH。为了比较镍和钯的醇盐的水解稳定性，我们用两种醇对两种氢氧化物进行了NMR滴定，并确定了相应的平衡常数。通常，这些常数约为。M = Ni比Pd小1个数量级，表明Ni醇盐配合物比Pd对应物更容易水解。对于含有无杂原子的R基团的醇盐配合物，随着母体醇ROH变得更酸性，其水解趋势降低，即R =

  DOI：

  10.1021/acs.inorgchem.7b01868
• 作为产物：
  描述：

  [1,3-亚苯基二(亚甲基)]二(二异丙基膦) 、 乙二醇二甲醚溴化镍 在 triethylamine 作用下， 以 四氢呋喃 为溶剂， 以90%的产率得到[(2,6-bis(diisopropylphosphinomethyl)phenyl)Ni-Br]
  参考文献：
  名称：

  镍和氟化钯配合物与PCP夹配体的合成及反应活性。基于NMR的氟化物和其他单阴离子配体的电子定性性能评估

  摘要：

  [[ iPr PCP）ML]（M = Ni，Pd）类型的一系列配合物，包含2,6-双（二异丙基膦基甲基）苯基（iPr PCP）钳形配体和简单的单阴离子配体L（F，Cl，Br ，H，Me，Ph，NO 3和OTf）已合成并表征。氟化物衍生物[（iPr PCP）MF]由卤化物[（iPr PCP）MX]（M = Ni，X = Br； M = Pd，X = I）通过与AgF交换反应或通过质子分解制得Et 3 N·3HF（TREAT-HF）的甲基配合物[（iPr PCP）M-Me]的合成。对新配合物和先前报告的L = OH，OMe和NH 2的配合物的13 C NMR数据进行的调查揭示了可以直接与与Ni（II）和Pd（II）中心配位的阴离子配体L的电子性能直接相关的重要趋势。金属键合的ipso碳的13 C共振的化学位移对L的σ供电能力非常敏感，该能力按以下顺序增加：L = OTf> NO 3 > F> OAc>

  DOI：

  10.1021/om2009793

文献信息

• o-Semiquinonic PCP-pincer nickel complexes with alkyl substituents: versatile coordination sphere dynamics
  作者：Konstantin A. Kozhanov、Michael P. Bubnov、Vladimir K. Cherkasov、Nina N. Vavilina、Larisa Yu. Efremova、Oleg. I. Artyushin、Irina L. Odinets、Gleb A. Abakumov

  DOI：10.1039/b801350k

  日期：——

  o-Semiquinonic nickel pincer complexes (R2PCP)Ni(SQ) show a versatile coordination sphere dynamics via "swing" or "fan" oscillations depending on the steric properties of the phosphorus substituents.

  邻-半喹诺酮镍钳配合物（R2PCP）Ni（SQ）根据磷取代基的空间特性，通过“摆动”或“扇形”振荡显示出多种配位球动力学。
• 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
• Preparation and Reactivities of PCP-Type Pincer Complexes of Nickel. Impact of Different Ligand Skeletons and Phosphine Substituents
  作者：Annie Castonguay、André L. Beauchamp、Davit Zargarian

  DOI：10.1021/om8005454

  日期：2008.11.10

  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.
• One-Pot Synthesis of 1,3-Bis(phosphinomethyl)arene PCP/PNP Pincer Ligands and Their Nickel Complexes
  作者：Wei-Chun Shih、Oleg V. Ozerov

  DOI：10.1021/acs.organomet.5b00671

  日期：2015.9.28

  A one-pot synthesis of arene-based PCP/PNP ligands has been developed. The reaction of 1,3-bis(bromomethyl)benzene or 2,6-bis(bromomethyl)pyridine with various chlorophosphines in acetonitrile afforded bis-phosphonium salts. These salts can then be reduced by magnesium powder to yield PCP or PNP ligands. In comparison to traditional synthetic methods for making PCP/PNP ligands involving the use of secondary phosphines, this new alternative method allows for the use of chlorophosphines, which are cheaper, safer to handle, and have a broader range of commercially available derivatives. This is especially true for the chlorophosphines with less bulky alkyl groups. Moreover, the one-pot procedure can be extended to allow for the direct synthesis of PCP/PNP nickel complexes. By using nickel powder as the reductant, the resulting nickel halide was found to directly undergo metalation with the PCP or PNP ligand to generate nickel complexes in high yields.