carbonyl hydridoformate bis[2-(diisopropylphosphino)ethyl]amine iron(II) | 1616980-27-8

• 英文名称: carbonyl hydridoformate bis[2-(diisopropylphosphino)ethyl]amine iron(II)
• 英文别名: Fe(II)(bis(2-(diisopropylphosphino)ethyl)amine)(CO)(H)(OC(O)H)
• CAS: 1616980-27-8
• 化学式: C₁₈H₃₉FeNO₃P₂
• 分子量: 435.307
• InChiKey: RSKACJGORZAUNH-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：

  carbonyl hydridoformate bis[2-(diisopropylphosphino)ethyl]amine iron(II) 在 lithium tetrafluoroborate 、 三苯基氧化膦 作用下， 以 1,4-二氧六环 为溶剂， 80.0 ℃ 、101.33 kPa 条件下， 生成
  参考文献：
  名称：

  Lewis Acid-Assisted Formic Acid Dehydrogenation Using a Pincer-Supported Iron Catalyst

  摘要：

  Formic acid (FA) is an attractive compound for H-2 storage. Currently, the most active catalysts for FA dehydrogenation use precious metals. Here, we report a homogeneous iron catalyst that, when used with a Lewis acid (LA) co-catalyst, gives approximately 1,000,000 turnovers for FA dehydrogenation. To date, this is the highest turnover number reported for a first-row transition metal catalyst. Preliminary studies suggest that the LA assists in the decarboxylation of a key iron formate intermediate and can also be used to enhance the reverse process of CO2 hydrogenation.

  DOI：

  10.1021/ja505241x
• 作为产物：
  描述：

  甲酸 、 [bis({2-[bis(propan-2-yl)phosphanyl]ethyl})amide](carbonyl)(hydride)iron(II) 以 四氢呋喃 为溶剂， 反应 0.17h， 以78%的产率得到carbonyl hydridoformate bis[2-(diisopropylphosphino)ethyl]amine iron(II)
  参考文献：
  名称：

  Lewis Acid-Assisted Formic Acid Dehydrogenation Using a Pincer-Supported Iron Catalyst

  摘要：

  Formic acid (FA) is an attractive compound for H-2 storage. Currently, the most active catalysts for FA dehydrogenation use precious metals. Here, we report a homogeneous iron catalyst that, when used with a Lewis acid (LA) co-catalyst, gives approximately 1,000,000 turnovers for FA dehydrogenation. To date, this is the highest turnover number reported for a first-row transition metal catalyst. Preliminary studies suggest that the LA assists in the decarboxylation of a key iron formate intermediate and can also be used to enhance the reverse process of CO2 hydrogenation.

  DOI：

  10.1021/ja505241x
• 作为试剂：
  描述：

  甲醇 在 lithium tetrafluoroborate 、 carbonyl hydridoformate bis[2-(diisopropylphosphino)ethyl]amine iron(II) 作用下， 以 乙酸乙酯 为溶剂， 反应 4.42h， 以99%的产率得到甲酸甲酯
  参考文献：
  名称：

  Base-Free Methanol Dehydrogenation Using a Pincer-Supported Iron Compound and Lewis Acid Co-catalyst

  摘要：

  Hydrogen is an attractive alternative energy vector to fossil fuels if effective methods for its storage and release can be developed. In particular, methanol, with a gravimetric hydrogen content of 12.6%, is a promising target for chemical hydrogen storage. To date, there are relatively few homogeneous transition metal compounds that catalyze the aqueous phase dehydrogenation of methanol to release hydrogen and carbon dioxide. In general, these catalysts utilize expensive precious metals and require a strong base. This paper shows that a pincer-supported Fe compound and a co-catalytic amount of a Lewis acid are capable of catalyzing base-free aqueous phase methanol dehydrogenation with turnover numbers up to 51 000. This is the highest turnover number reported for either a first-row transition metal or a base-free system. Additionally, this paper describes preliminary mechanistic experiments to understand the reaction pathway and propose a stepwise process, which requires metal ligand cooperativity. This pathway is supported by DFT calculations and explains the role of the Lewis acid co-catalyst.

  DOI：

  10.1021/acscatal.5b00137

文献信息

• Understanding the Reactivity and Decomposition of a Highly Active Iron Pincer Catalyst for Hydrogenation and Dehydrogenation Reactions
  作者：Julia B. Curley、Nicholas E. Smith、Wesley H. Bernskoetter、Mehmed Z. Ertem、Nilay Hazari、Brandon Q. Mercado、Tanya M. Townsend、Xiaoping Wang

  DOI：10.1021/acscatal.1c03347

  日期：2021.8.20

  pathways through which catalytic intermediates related to 1 and 2 undergo decomposition. This involved characterizing the unstable and previously unobserved complexes [(iPrPNHP)Fe(H)(CO)(L)]+ (5-L; L = THF or N2) and [(iPrPNHP)Fe(H)(H2)(CO)]+ (8), which are proposed as intermediates when 1 and 2 are used as catalysts. Compound 8 was synthesized through the reaction of (iPrPNHP)Fe(H)(CO)(PF6) (6) with

  铁钳络合物 ( iPr PNP)Fe(H)(CO) ( 1 , iPr PNP – = N(CH 2 CH 2 PiPr 2 ) 2 – ) 是许多加氢和脱氢反应的活性（预）催化剂。这部分是因为1可以可逆地添加H. 2穿过铁酰胺键的形式（的iPr PN ħ P）的Fe（H）2（CO）（2，的iPr PN ħ P = HN（CH 2 CH 2 P我镨2 ) 2）。然而，快速分解限制了1和相关配合物的催化性能。我们探索了与1和2相关的催化中间体进行分解的途径。这涉及表征不稳定的和以前未观察到的复合物 [( iPr PN H P)Fe(H)(CO)(L)] + ( 5-L ; L = THF 或 N 2 ) 和 [( iPr PN H P)Fe( H)(H 2 )(CO)] + ( 8 )，当1和2用作催化剂时，建议将其用作中间体。化合物8通过（的反应合成的iPr PN ħ P）的Fe（H）（CO）（PF