[2,6-(^tBu₂PO)₂C₆H₃]Ni(η²-BH₄) | 1378876-13-1

• 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]Ni(η²-BH₄)
• 英文别名: boranuide;ditert-butyl-(3-ditert-butylphosphanyloxybenzene-2-id-1-yl)oxyphosphane;nickel(2+)
• CAS: 1378876-13-1
• 化学式: C₂₂H₄₃BNiO₂P₂
• 分子量: 471.031
• InChiKey: BIXHDBMPVQTVPD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.78
• 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]Ni(η²-BH₄) 以 neat (no solvent, solid phase) 为溶剂， 反应 24.0h， 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：

  [2,6-(^tBu₂PO)₂C₆H₃]NiCl 以 四氢呋喃 、 氘代苯 、 甲苯 为溶剂， 反应 0.5h， 生成 [2,6-(^tBu₂PO)₂C₆H₃]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。
• Hydroboration of CO₂ catalyzed by bis(phosphinite) pincer ligated nickel thiolate complexes
  作者：Ting Liu、Wenjuan Meng、Qiang-Qiang Ma、Jie Zhang、Huizhen Li、Shujun Li、Qianyi Zhao、Xuenian Chen

  DOI：10.1039/c7dt00490g

  日期：——

  We report the hydroboration of CO2 with catecholborane catalyzed by a series of bis(phosphinite) pincer ligated nickel thiolate complexes. Turnover frequencies (TOFs) up to 2400 h−1 were achieved at room temperature under an atmospheric pressure of CO2. This represents the highest TOF value known to date for the reduction of CO2 to the methoxide level under mild conditions.

  我们报告了一系列的双（次膦酸酯）钳连接硫醇镍配合物催化的儿茶酚硼烷CO 2的硼氢化。在室温和CO 2的大气压下，可实现高达2400 h -1的周转频率（TOF）。这代表了迄今已知的在温和条件下将CO 2还原为甲醇盐含量的最高TOF值。
• A reaction of [2,6-(^tBu₂PO)₂C₆H₃]NiSCH₂Ph with BH₃·THF: borane mediated C–S bond cleavage
  作者：Jie Zhang、Ting Liu、Qiang-Qiang Ma、Shujun Li、Xuenian Chen

  DOI：10.1039/c7dt04883a

  日期：——

  metathesis reaction of the corresponding chloride complex with NaSH and fully characterized by multinuclear NMR, FTIR, HRMS, X-ray crystallography and elemental analysis. A possible mechanism for the formation of 5 was proposed. It was supposed that 5 formed through BH3 mediated C–S bond cleavage of the thiolato ligand of 1. The result would initiate further studies on the transition metal catalyzed

  硫酚和硫醇的C–S键活化非常重要，但鲜有报道。在本文中，我们报道了由BH 3 ·THF介导的[2,6-（t Bu 2 PO）2 C 6 H 3 ] NiSCH 2 Ph（1）的巯基配体的C–S键裂解。治疗1用过量的BH 3在THF·THF在室温下，得到的硼氢化物[2,6-（吨卜2 PO）2 C ^ 6 ħ 3 ]的Ni（η 2 -BH 4）（2）作为唯一产品​​。1与2当量的反应。室温下，在THF中将BH 3 ·THF溶解48 h，生成氢化物络合物[2,6-（t Bu 2 PO）2 C 6 H 3 ] NiH（3）和巯基络合物[2,6-（t Bu 2 PO）2 C 6 H 3 ] NiSH（5）。作为一个新的综合体，5还通过相应的氯化物络合物与NaSH的盐复分解反应独立合成了Sn，并通过多核NMR，FTIR，HRMS，X射线晶体学和元素分析对其进行了全面表征。提出了形成5的可能机理。推测5是通过BH