[2,6-(^tBu₂PO)₂C₆H₃]NiCl | 1108747-38-1

• 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: [2,6-(^tBu₂PO)₂C₆H₃]NiCl
• 英文别名: ditert-butyl-(3-ditert-butylphosphanyloxybenzene-2-id-1-yl)oxyphosphane;nickel(2+);chloride
• CAS: 1108747-38-1
• 化学式: C₂₂H₃₉ClNiO₂P₂
• 分子量: 491.641
• InChiKey: GJEXNEFLSCCRTR-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  5.23
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [2,6-(^tBu₂PO)₂C₆H₃]NiCl 以 氘代苯 为溶剂， 生成 [(tert-butyl)2POC6H3OP(tert-butyl)2]NiH
  参考文献：
  名称：

  Pincer-Ligated Nickel Hydridoborate Complexes: the Dormant Species in Catalytic Reduction of Carbon Dioxide with Boranes

  摘要：

  Nickel pincer complexes of the type [2,6-(R2PO)(2)C6H3]NiH (R = Bu-t, 1a; R = Pr-i, 1b; R = (c)Pe, 1c) react with BH3 center dot THF to produce borohydride complexes [2,6-(R2PO)(2)C6H3]Ni(eta(2)-BH4) (2a-c), as confirmed by NMR and IR spectroscopy, X-ray crystallography, and elemental analysis. The reactions are irreversible at room temperature but reversible at 60 degrees C. Compound 1a exchanges its hydrogen on the nickel with the borane hydrogen of 9-BBN or HBcat, but does not form any observable adduct. The less bulky hydride complexes 1b and 1c, however, yield nickel dihydridoborate complexes reversibly at room temperature when mixed with 9-BBN and HBcat. The dihydridoborate ligand in these complexes adopts an eta(2)-coordination mode, as suggested by ER. spectroscopy and X-ray crystallography. Under the catalytic influence of 1a-c, reduction of CO2 leads to the methoxide level when 9-BBN or HBcat is employed as the reducing agent. The best catalyst, 1a, involves bulky substituents on the phosphorus donor atoms. Catalytic reactions involving 1b and 1c are less efficient because of the formation of dihydridoborate complexes as the dormant species as well as partial decomposition of the catalysts by the boranes.

  DOI：

  10.1021/ic300587b
• 作为产物：
  描述：

  二叔丁基氯化膦 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 [2,6-(^tBu₂PO)₂C₆H₃]NiCl
  参考文献：
  名称：

  Rapid oxidative hydrogen evolution from a family of square-planar nickel hydride complexes

  摘要：

  在一系列方形平面镍氢化物配合物中进行单电子氧化会导致轻松的H₂生成。

  DOI：

  10.1039/c5sc03189c

文献信息

• 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。
• 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）
• Hydrosilylation of Aldehydes and Ketones Catalyzed by Nickel PCP-Pincer Hydride Complexes
  作者：Sumit Chakraborty、Jeanette A. Krause、Hairong Guan

  DOI：10.1021/om800948f

  日期：2009.1.26

  Nickel PCP-pincer hydride complexes catalyze chemoselective hydrosilylation of C═O bonds of aldehydes and ketones in the presence of other functional groups. The mechanism involves C═O insertion into a nickel−hydrogen bond, followed by cleavage of the newly formed Ni−O bond with a silane.

  在其他官能团存在的情况下，镍PCP钳式氢化物配合物催化醛和酮的C═O键的化学选择性氢化硅烷化。其机理包括将C = O插入镍氢键中，然后用硅烷裂解新形成的Ni-O键。
• A Comparative Study on the Thermodynamics of Halogen Bonding of Group 10 Pincer Fluoride Complexes
  作者：Markus Joksch、Hemlata Agarwala、Monica Ferro、Dirk Michalik、Anke Spannenberg、Torsten Beweries

  DOI：10.1002/chem.201904863

  日期：2020.3.18

  The thermodynamics of halogen bonding of a series of isostructural Group 10 metal pincer fluoride complexes of the type [(3,5-R2 -tBu POCOPtBu )MF] (3,5-R2 -tBu POCOPtBu =κ3 -C6 HR2 -2,6-(OPtBu2 )2 with R=H, tBu, COOMe; M=Ni, Pd, Pt) and iodopentafluorobenzene was investigated. Based on NMR experiments at different temperatures, all complexes 1-tBu (R=tBu, M=Ni), 2-H (R=H, M=Pd), 2-tBu (R=tBu, M=Pd)

  [[3,5-R2 -tBu POCOPtBu）MF]（3,5-R2 -tBu POCOPtBu =κ3-C6 HR2 -2,6研究了具有（R ＝ H，tBu，COOMe； M ＝ Ni，Pd，Pt）和碘五氟苯的-（OPtBu 2）2。根据不同温度下的NMR实验，所有配合物1-tBu（R = tBu，M = Ni），2-H（R = H，M = Pd），2-tBu（R = tBu，M = Pd），2 -COOMe（R = COOMe，M = Pd）和3-tBu（R = tBu，M = Pt）与Pd配合物形成强卤素键，显示出与碘五氟苯的明显更强的结合力。甲苯溶液中2-tBu与1,4-二碘四氟苯配合物的模型加合物以及碘五氟苯的结构的结构和计算分析表明，形成了I型接触。
• The Reactivity of Mercapto Groups against Boron Hydrides in Pincer Ligated Nickel Mercapto Complexes
  作者：Jie Zhang、Ting Liu、Changgeng Wei、Jiarui Chang、Qiang-Qiang Ma、Shujun Li、Nana Ma、Xuenian Chen

  DOI：10.1002/asia.201801050

  日期：2018.11.2

  boron hydrides or organic bases. The treatment of complex 2 a or 2 b with an excess amount of catecholborane (HBcat) afforded the corresponding pincer ligated nickel borohydride complexes and the HBcat degradation product. The treatment of complex 1 a, 2 a or 2 b with an excess amount of BH3⋅THF produced the corresponding nickel borohydride species and the S‐bridged triborane species THF⋅BH2‐μ2‐S(B2H5)

  几种钳形连接的巯基镍配合物[2,6-（R 2 PCH 2）2 C 6 H 3 ] NiSH（R = t Bu，1 a ; i Pr，1 b），[2,6-（R 2 PO ）2 C 6 H 3 ] NiSH（R = t Bu，2 a ; i Pr，2 b）和[4-MeOCO-2,6-（t Bu 2 PO）2 C 6 H 2 ] NiSH（3 a），进行了合成并进行了充分表征。研究了巯基对氢化硼和有机碱的反应性。发现巯基很难被氢化硼或有机碱去质子化。复合物的治疗 2或2b中与过量的量的儿茶酚硼烷（HBcat），得到相应的钳结扎硼氢化镍络合物和HBcat降解产物。的复杂的处理 1，2或图2b与BH过量3 ⋅THF产生相应的硼氢化镍物种和S-桥接triborane物种THF⋅BH 2 - μ 2 -S（B2 H 5）（5）。在这些配合物和有机碱之间未观察到反应。进行DFT计算是为了了解这种反应性并获得对反应的机械见解。