(iPrPOCOP)Ni(η2-BH4) | 1378876-20-0

• 英文名称: (iPrPOCOP)Ni(η2-BH4)
• 英文别名: [2,6-(iPr₂PO)₂C₆H₃]Ni(BH₄)；(^iPrPOCOP)Ni(η²-BH₄)
• CAS: 1378876-20-0
• 化学式: C₁₈H₃₅BNiO₂P₂
• 分子量: 414.923
• InChiKey: QOFIDOVHKVLACY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  二氧化碳 、 (iPrPOCOP)Ni(η2-BH4) 以 氘代苯 为溶剂， 60.0 ℃ 、101.33 kPa 条件下， 反应 48.0h， 生成 [(isopropyl)2POC6H3OP(isopropyl)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：

  以 四氢呋喃 、 氘代甲苯 、 甲苯 为溶剂， 反应 0.5h， 生成 (iPrPOCOP)Ni(η2-BH4)
  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

文献信息

• 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。