{2,6-(tBu₂PO)₂C₆H₃}Ni(OCHO) | 1229029-81-5

• 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}Ni(OCHO)
• 英文别名: [(tert-butyl)2POC6H3OP(tert-butyl)2]Ni(formate)；ditert-butyl-(3-ditert-butylphosphanyloxybenzene-2-id-1-yl)oxyphosphane;nickel(2+);formate
• CAS: 1229029-81-5
• 化学式: C₂₃H₄₀NiO₄P₂
• 分子量: 501.206
• InChiKey: FSIHILBJJWLGOA-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  30
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  58.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  {2,6-(tBu₂PO)₂C₆H₃}Ni(OCHO) 以 氘代甲苯 、 甲苯 为溶剂， 反应 20.0h， 生成
  参考文献：
  名称：

  Using CS₂ to Probe the Mechanistic Details of Decarboxylation of Bis(phosphinite)-Ligated Nickel Pincer Formate Complexes

  摘要：

  The reaction of the formate complex {2,6-(R2PO)(2)C6H3}Ni(OCHO) (R = Bu-t, 5; R = Pr-i, 6) with CS2 shows first-order kinetics in nickel concentration and zero-order in [CS2] when CS2 is used in large excess. Rate measurement at different temperatures gives activation parameters Delta H* = 22.6 +/- 0.9 kcal/mol and Delta S* = -5.2 +/- 3.0 eu for the decarboxylation of 5 and Delta H* = 22.6 +/- 1.0 kcal/mol and Delta S* = -4.3 +/- 3.2 eu for the decarboxylation of 6. Comparing the decarboxylation rate constants for 6 and {2,6-((Pr2PO)-Pr-i)(2)C6H3}Ni(OCDO) (6-d) yields KIE values of 1.67-1.90 within the temperature range 30-45 degrees C. On the basis of these experimental results and DFT calculations, an ion pair mechanism has been proposed for the decarboxylation process. The CS2 insertion products {2,6-(R2PO)(2)C6H3}Ni-(SCHS)(R = Bu-t, 3; R = Pr-i, 4) have been characterized by X-ray crystallography.

  DOI：

  10.1021/acs.organomet.6b00759
• 作为产物：
  描述：

  二氧化碳 、 以 not given 为溶剂， 生成 {2,6-(tBu₂PO)₂C₆H₃}Ni(OCHO)
  参考文献：
  名称：

  An Efficient Nickel Catalyst for the Reduction of Carbon Dioxide with a Borane

  摘要：

  Nickel hydride with a diphosphinite-based ligand catalyzes the highly efficient reduction of CO(2) with catecholborane, and the hydrolysis of the resulting methoxyboryl species produces CH(3)OH in good yield. The mechanism involves a nickel formate, formaldehyde, and a nickel methoxide as different reduced stages for CO(2). The reaction may also be catalyzed by an air-stable nickel formate.

  DOI：

  10.1021/ja103982t

文献信息

• Catalytic properties of nickel bis(phosphinite) pincer complexes in the reduction of CO2 to methanol derivatives
  作者：Sumit Chakraborty、Yogi J. Patel、Jeanette A. Krause、Hairong Guan

  DOI：10.1016/j.poly.2011.04.030

  日期：2012.1

  however, it reacts with 9-borabicyclo[3.3.1]nonane and pinacolborane to generate a methanol derivative and a boryl formate species, respectively. The catalytic reduction of CO 2 with catecholborane is more effectively catalyzed by a more sterically hindered nickel pincer hydride complex with bulky R groups on the phosphorus donor atoms. The nickel pincer hydride complexes are inactive catalysts for

  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
• Pincer-Ligated Nickel Hydridoborate Complexes: the Dormant Species in Catalytic Reduction of Carbon Dioxide with Boranes
  作者：Sumit Chakraborty、Jie Zhang、Yogi J. Patel、Jeanette A. Krause、Hairong Guan

  DOI：10.1021/ic300587b

  日期：2013.1.7

  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.