[(tert-butyl)2POC6H3OP(tert-butyl)2]NiH | 1108747-41-6

• 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: [(tert-butyl)2POC6H3OP(tert-butyl)2]NiH
• 英文别名: catecholborane；[2,6-(^tBu₂PO)₂C₆H₃]NiH；(^tBuPOCOP)NiH
• CAS: 1108747-41-6
• 化学式: C₂₂H₄₀NiO₂P₂
• 分子量: 457.196
• InChiKey: BWPKZFUWHQCCNC-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：
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• 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：

  [(tert-butyl)2POC6H3OP(tert-butyl)2]NiH 以 氘代甲苯 、 甲苯 为溶剂， 反应 2.0h， 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：

  [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
• 作为试剂：
  描述：

  二氧化碳 、 儿萘酚硼烷 在 [(tert-butyl)2POC6H3OP(tert-butyl)2]NiH 作用下， 以 氘代苯 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 0.75h， 生成 catecholborane 、 bis(catecholboryl) oxide
  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

• Fundamental organometallic chemistry under bimetallic influence: driving β-hydride elimination and diverting migratory insertion at Cu and Ni
  作者：Thomas J. Mazzacano、Noel J. Leon、Greyson W. Waldhart、Neal P. Mankad

  DOI：10.1039/c6dt04533b

  日期：——

  Bimetallic effects on stoichiometric β-hydride elimination and migratory insertion reactions were examined. Bimetallic reaction conditions drove β-hydride elimination at Cu, while bimetallic C–B elimination occurred in the absence of β-hydrogens. The inherent migratory insertion chemistry of alkynes at Ni was diverted under bimetallic reaction conditions to favor C–H deprotonation.

  研究了双金属对化学计量β-氢化物消除和迁移插入反应的影响。双金属反应条件驱使Cu处的β-氢化物消除，而双金属C–B的消除是在不存在β氢的情况下发生的。在双金属反应条件下，炔烃在Ni上固有的迁移插入化学被转移为有利于CH去质子化。
• 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
• An Efficient Nickel Catalyst for the Reduction of Carbon Dioxide with a Borane
  作者：Sumit Chakraborty、Jie Zhang、Jeanette A. Krause、Hairong Guan

  DOI：10.1021/ja103982t

  日期：2010.7.7

  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.