Sequential Hydrogenation of CO<sub>2</sub> to Methanol Using a Pincer Iron Catalyst

Lane, Elizabeth M.; Zhang, Yuanyuan; Hazari, Nilay; Bernskoetter, Wesley H.

doi:10.1021/acs.organomet.9b00413

Cited by 63 publications

(51 citation statements)

References 54 publications

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“…The first one was morphylcarbamate, a counter-anion, which forms upon the morpholine reaction with carbon dioxide. This reaction was hardly without precedence [37][38][39][40][41].…”

Section: Synthetic Considerationsmentioning

confidence: 97%

Beyond the Simple Copper(II) Coordination Chemistry with Quinaldinate and Secondary Amines

2020

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Copper(II) acetate has reacted in methanol with quinaldinic acid (quinoline-2-carboxylic acid) to form [Cu(quin)2(CH3OH)]∙CH3OH (1) (quin− = an anionic form of the acid) with quinaldinates bound in a bidentate chelating manner. In the air, complex 1 gives off methanol and binds water. The conversion was monitored by IR spectroscopy. The aqua complex has shown a facile substitution chemistry with alicyclic secondary amines, pyrrolidine (pyro), and morpholine (morph). trans-[Cu(quin)2(pyro)2] (2) and trans-[Cu(quin)2(morph)2] (4) were obtained in good yields. The morpholine system has produced a by-product, trans-[Cu(en)2(H2O)2](morphCOO)2 (5) (morphCOO− = morphylcarbamate), a result of the copper(II) quinaldinate reaction with ethylenediamine (en), an inherent impurity in morpholine, and the amine reaction with carbon dioxide. (pyroH)[Cu(quin)2Cl] (3) forms on the recrystallization of [Cu(quin)2(pyro)2] from dichloromethane, confirming a reaction between amine and the solvent. Similarly, a homologous amine, piperidine (pipe), and dichloromethane produced (pipeH)[Cu(quin)2Cl] (11). The piperidine system has afforded both mono- and bis-amine complexes, [Cu(quin)2(pipe)] (6) and trans-[Cu(quin)2(pipe)2] (7). The latter also exists in solvated forms, [Cu(quin)2(pipe)2]∙CH3CN (8) and [Cu(quin)2(pipe)2]∙CH3CH2CN (9). Interestingly, only the piperidine system has experienced a reduction of copper(II). The involvement of amine in the reduction was undoubtedly confirmed by identification of a polycyclic piperidine compound 10, 6,13-di(piperidin-1-yl)dodecahydro-2H,6H-7,14-methanodipyrido[1,2-a:1′,2′-e][1,5]diazocine.

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“…The first one was morphylcarbamate, a counter-anion, which forms upon the morpholine reaction with carbon dioxide. This reaction was hardly without precedence [37][38][39][40][41].…”

Section: Synthetic Considerationsmentioning

confidence: 97%

Beyond the Simple Copper(II) Coordination Chemistry with Quinaldinate and Secondary Amines

2020

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“…Owing to the increasing interest in replacing precious metals by base metals, and taking into account the opportunity that metal-ligand cooperation affords in this direction, the groups of Prakash 113 and Bernskoetter 114 reported two Mn and Fe [PNP] complexes, respectively, for the MeOH synthesis from CO 2 through formamide hydrogenation. Unfortunately, both catalytic systems deactivated in the one-pot procedure.…”

Section: Related Catalytic Hydrogenative Transformationsmentioning

confidence: 99%

Homogeneous and heterogeneous catalytic reduction of amides and related compounds using molecular hydrogen

et al. 2020

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Catalytic hydrogenation of amides is of great interest for chemists working in organic synthesis, as the resulting amines are widely featured in natural products, drugs, agrochemicals, dyes, etc. Compared to traditional reduction of amides using (over)stoichiometric reductants, the direct hydrogenation of amides using molecular hydrogen represents a greener approach. Furthermore, amide hydrogenation is a highly versatile transformation, since not only higher amines (obtained by CO cleavage), but also lower amines and alcohols, or amino alcohols (obtained by C-N cleavage) can be selectively accessed by fine tuning of reaction conditions. This review describes the most recent advances in the area of amide hydrogenation using H 2 exclusively and molecularly defined homogeneous as well as nanostructured heterogeneous catalysts, with a special focus on catalyst development and synthetic applications. T he development of green and sustainable methods is a central focus of modern organic synthesis and its applications in various areas of the chemical industry. In this respect, many reduction reactions, traditionally employing stoichiometric amounts of metal hydrides with inherent low atom efficiency 1 , can be favorably replaced by catalytic hydrogenations. In fact, the combination of molecular hydrogen and catalysts does not only allow avoiding formation of waste products 2 , it also opens the door to clean transformations based on renewable energies as the conversion of solar or wind energy to "green" hydrogen is likely to be implemented in the coming years. Among the many reduction reactions known, amide hydrogenation can be encountered as one of the most desired considering the importance of the derived amines in several branches of chemical industry. In fact, since the start of the Green Chemistry Institute Pharmaceutical Roundtable in the United States in 2005, several projects aimed to the achievement of a practical amide hydrogenation methodology have been supported 3,4. The long-term interest of the pharmaceutical industry in this specific transformation is explained by the fact that it ideally affords structurally complex amines, present in many of the currently employed drugs. Furthermore, amines are also in bulk and fine chemicals used in the manufacture of plastics, textiles, surfactants, dyes, and many more 5. Amides play a central role in the chemistry of life, as they are the key elements to generate peptides and proteins from amino acid monomers. At the same time, they are present in artificial

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“…Although people have achieved some progresses in homogeneous catalytic hydrogenation of CO 2 with the development of base metal iron [15][16][17], cobalt [18], and manganese [19] catalysts in recent years, most of the experimentally reported efficient CO 2 hydrogenation catalysts contain noble metals and air-and moisture-sensitive phosphine ligands [6,[20][21][22][23][24][25][26][27][28][29][30][31][32]. For the catalytic hydrogenation of CO 2 to methanol reaction, only a few base metal catalysts are reported so far.…”

Section: Introductionmentioning

confidence: 99%

“…Pombeiro and co-workers [16] reported direct synthesis of methanol from CO2 and H2 catalyzed by an Fe(II) scorpionate complex achieved 44% yield of methanol with TONs and turnover frequencies (TOFs) up to 2387 and 167 h −1 , respectively, at 80 °C and 75 pressure. Bernskoetter and co-workers [17] reported an Fe(II) pincer complex for homogeneously catalytic conversion of H2 and CO2 to methanol with 250 psi of CO2 and 1150 psi of H2 at 100 °C with a TON of 590. Prakash and co-workers [19] investigated phosphorus-nitrogen-phosphorus (PNP) manganese pincer complexes for homogeneous hydrogenation of CO2 to methanol at 80 bar and 150 °C with TONs up to 36.…”

Section: Introductionmentioning

confidence: 99%

Bioinspired Design and Computational Prediction of SCS Nickel Pincer Complexes for Hydrogenation of Carbon Dioxide

2020

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Inspired by the structures of the active site of lactate racemase and H2 activation mechanism of mono-iron hydrogenase, we proposed a series of sulphur–carbon–sulphur (SCS) nickel complexes and computationally predicted their potentials for catalytic hydrogenation of CO2. Density functional theory calculations reveal a metal–ligand cooperated mechanism with the participation of a sulfur atom in the SCS pincer ligand as a proton receiver for the heterolytic cleavage of H2. For all newly proposed complexes containing functional groups with different electron-donating and withdrawing abilities in the SCS ligand, the predicted free energy barriers for the hydrogenation of CO2 to formic acid are in a range of 22.2–25.5 kcal/mol in water. Such a small difference in energy barriers indicates limited contributions of those functional groups to the charge density of the metal center. We further explored the catalytic mechanism of the simplest model complex for hydrogenation of formic acid to formaldehyde and obtained a total free energy barrier of 34.6 kcal/mol for the hydrogenation of CO2 to methanol.

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Sequential Hydrogenation of CO₂ to Methanol Using a Pincer Iron Catalyst

Cited by 63 publications

References 54 publications

Beyond the Simple Copper(II) Coordination Chemistry with Quinaldinate and Secondary Amines

Beyond the Simple Copper(II) Coordination Chemistry with Quinaldinate and Secondary Amines

Homogeneous and heterogeneous catalytic reduction of amides and related compounds using molecular hydrogen

Bioinspired Design and Computational Prediction of SCS Nickel Pincer Complexes for Hydrogenation of Carbon Dioxide

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Sequential Hydrogenation of CO2 to Methanol Using a Pincer Iron Catalyst

Cited by 63 publications

References 54 publications

Beyond the Simple Copper(II) Coordination Chemistry with Quinaldinate and Secondary Amines

Beyond the Simple Copper(II) Coordination Chemistry with Quinaldinate and Secondary Amines

Homogeneous and heterogeneous catalytic reduction of amides and related compounds using molecular hydrogen

Bioinspired Design and Computational Prediction of SCS Nickel Pincer Complexes for Hydrogenation of Carbon Dioxide

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Product

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Sequential Hydrogenation of CO₂ to Methanol Using a Pincer Iron Catalyst