(cyclopentylPOCOP)NiH | 1354969-51-9

• 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: (cyclopentylPOCOP)NiH
• 英文别名: (^cyclopentylPOCOP)NiH；(^cPePOCOP)NiH；[(cyclopentyl)2POC6H3OP(cyclopentyl)2]NiH
• CAS: 1354969-51-9
• 化学式: C₂₆H₄₀NiO₂P₂
• 分子量: 505.24
• InChiKey: NPDVSSXDWHVMII-UHFFFAOYSA-N

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：

  (cyclopentylPOCOP)NiH 以 四氢呋喃 、 氘代苯 、 甲苯 为溶剂， 60.0 ℃ 、101.33 kPa 条件下， 反应 48.5h， 生成 [(cyclopentyl)2POC6H3OP(cyclopentyl)2]Ni(formate)
  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：

  (cyclopentylPOCOP)Ni(μ-H)2(9-borabicyclo(3.3.1)nonane) 以 neat (no solvent, solid phase) 为溶剂， 反应 1.0h， 生成 (cyclopentylPOCOP)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
• 作为试剂：
  描述：

  二氧化碳 、 儿萘酚硼烷 在 (cyclopentylPOCOP)NiH 作用下， 以 氘代苯 为溶剂， 生成 catecholborane
  参考文献：
  名称：

  双亚膦酸酯镍配合物在将CO2还原为甲醇衍生物中的催化性能

  摘要：

  摘要用间苯二酚ClP（C 5 H 9）在一个罐中制备了一种新的镍双（亚膦酸酯）夹钳络合物[2,6-（R 2 PO）2 C 6 H 3] NiCl（LR NiCl，R =环戊基） ）2，NiCl 2和4-二甲基氨基吡啶。该夹钳化合物与LiAlH 4的反应产生氢化镍配合物，其能够在室温下快速还原CO 2以得到甲酸镍配合物。两种相关的甲酸镍配合物LR NiOCHO（R =环戊基和异丙基）的X射线结构显示了甲酰基相对于配位平面的“面内”构象。甲酸镍配合物LR NiOCHO（R =环戊基，异丙基和叔丁基）与儿茶酚硼烷的化学计量反应表明，庞大的R基团有助于该反应。LR NiOCHO（R =叔丁基）在室温下不与PhSiH 3反应；但是，它会与9-borabicyclo [3.3.1]壬烷和频哪醇硼烷反应，分别生成甲醇衍生物和甲酸硼基酯。邻苯二酚硼烷对CO 2的催化还原作用更有效地由位阻更大的磷供体原子上

  DOI：

  10.1016/j.poly.2011.04.030

文献信息

• Reactions of phenylacetylene with nickel POCOP-pincer hydride complexes resulting in different outcomes from their palladium analogues
  作者：Gleason L. O. Wilson、Medhanei Abraha、Jeanette A. Krause、Hairong Guan

  DOI：10.1039/c5dt00161g

  日期：——

  alkynyl complexes [2,6-(R2PO)2C6H3]NiCCPh (7a–b) and H2 are not produced in the nickel system. The more bulky hydride complex [2,6-(tBu2PO)2C6H3]NiH (4c) shows no reactivity towards phenylacetylene. Catalytic hydrogenation of phenylacetylene with 4a–b takes place at an elevated temperature (70–100 °C) and proves to be heterogeneous. The structures of 5b, 6a, 7a and 7b have been studied by X-ray crystallography

  POCOP钳形氢化镍镍配合物[2,6-（R 2 PO）2 C 6 H 3 ] NiH（R = i Pr，4a ; R = c Pe =环戊基，4b）与苯乙炔反应生成[2,6- （R 2 PO）2 C 6 H 3 ] NiC（Ph）CH 2（5a–b）为主要产物，而（E）-[2,6-（R 2 PO）2 C 6 H 3 ] NiCH CHPh（6a–b）作为次要产品。2,1插入比1,2插入更有利，并且两种途径都涉及通过C C键顺式添加Ni–H 。与钯不同，在镍体系中不会生成炔基络合物[2,6-（R 2 PO）2 C 6 H 3 ] NiC CPh（7a–b）和H 2。更大体积的氢化物配合物[2,6-（t Bu 2 PO）2 C 6 H 3 ] NiH（4c）对苯基乙炔没有反应性。4a–b催化苯乙炔加氢发生在高温下（70–100°C），并且证明是异质的。的结构图5b，图6a，图7a和7b中已经研究了通过X射线晶体学。