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Increasing carbon dioxide emissions has sparked a growing interest in capturing these emissions at the source of their release. For such processes, amines can be used as carbon dioxide capture agents. Herein, CO2 was captured under ambient conditions using solutions of amines and polyamines in ethylene glycol. The captured solutions were then successfully hydrogenated to methanol under hydrogen pressure with a heterogeneous Cu/ZnO/Al2O3 industrial catalyst. An extensive amine scope found that tetramethyl-1,6-hexanediamine, with two tertiary amine sites, provided the highest methanol productivity. This reaction was then optimized to achieve up to 89% methanol yield under relatively mild conditions of 250 °C and 80 bar H2 pressure. The catalyst was shown to be recyclable over five reaction cycles.
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An efficient method for the direct C(sp)-H difluoromethylation of terminal alkynes and the desilylation-difluoromethylation of (trimethylsilyl)acetylenes is disclosed. The copper-catalyzed transformation provides access to a wide range of structurally diverse CF2H alkynes in good yields, utilizing a (difluoromethyl)zinc reagent and an organic oxidant. The difluoromethylation of important synthons and API's is showcased. The synthetic utility of these (difluoromethyl)alkynes is demonstrated by selected cycloaddition reactions. Additionally, a slight modification to the reaction conditions allowed the selective preparation of a 2-difluoromethylindole.
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The first example of an alkali hydroxide-based system for CO2 capture and conversion to methanol has been established. Bicarbonate and formate salts were hydrogenated to methanol with high yields in a solution of ethylene glycol. In an integrated one-pot system, CO2 was efficiently captured by an ethylene glycol solution of the base and subsequently hydrogenated to CH3OH at relatively mild temperatures (100-140 °C) using Ru-PNP catalysts. The produced methanol can be easily separated by distillation. Hydroxide base regeneration at low temperatures was observed for the first time. Finally, CO2 capture from ambient air and hydrogenation to CH3OH was demonstrated. We postulate that the high capture efficiency and stability of hydroxide bases make them superior to existing amine-based routes for direct air capture and conversion to methanol in a scalable process.
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The capture of CO2 from concentrated emission sources as well as from air represents a process of paramount importance in view of the increasing CO2 concentration in the atmosphere and its associated negative consequences on the biosphere. Once captured using various technologies, CO2 is desorbed and compressed for either storage (carbon capture and storage (CCS)) or production of value-added products (carbon capture and utilization (CCU)). Among various products that can be synthesized from CO2, methanol and formic acid are of high interest because they can be used directly as fuels or to generate H2 on demand at low temperatures (<100 °C), making them attractive hydrogen carriers (12.6 and 4.4 wt % H2 in methanol and formic acid, respectively). Methanol is already produced in huge quantities worldwide (100 billion liters annually) and is also a raw material for many chemicals and products, including formaldehyde, dimethyl ether, light olefins, and gasoline. The production of methanol through chemical recycling of captured CO2 is at the heart of the so-called "methanol economy" that we have proposed with the late Prof. George Olah at our Institute. Recently, there has been significant progress in the low-temperature synthesis of formic acid (or formate salts) and methanol from CO2 and H2 using homogeneous catalysts. Importantly, several studies have combined CO2 capture and hydrogenation, where captured CO2 (including from air) was directly utilized to produce formate and CH3OH without requiring energy intensive desorption and compression steps. This Account centers on that topic. A key feature in the combined CO2 capture and conversion studies reported to date for the synthesis of formic acid and methanol is the use of an amine or alkali-metal hydroxide base for capturing CO2, which can assist the homogeneous catalysts in the hydrogenation step. We start this Account by examining the combined processes where CO2 is captured in amine solutions and converted to alkylammonium formate salts. The effect of amine basicity on the reaction rate is discussed along with catalyst recycling schemes. Next, methanol synthesis by this combined process, with amines as capturing agents, is explored. We also examine the system developments for effective catalyst and amine recycling in this process. We next go through the effect of catalyst molecular structure on methanol production while elucidating the main deactivating pathway involving carbonylation of the metal center. The recent advances in first-row transition metal catalysts for this process are also mentioned. Subsequently, we discuss the capture of CO2 using hydroxide bases and conversion to formate salts. The regeneration of the hydroxide base (NaOH or KOH) at low temperatures (80 °C) in cation-conducting direct formate fuel cells is presented. Finally, we review the challenges in the yet unreported integrated CO2 capture by hydroxide bases and conversion to methanol process.
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The methylamino diazonium cations [CH3 N(H)N2 ]+ and [CF3 N(H)N2 ]+ were prepared as their low-temperature stable [AsF6 ]- salts by protonation of azidomethane and azidotrifluoromethane in superacidic systems. They were characterized by NMR and Raman spectroscopy. Unequivocal proof of the protonation site was obtained by the crystal structures of both salts, confirming the formation of alkylamino diazonium ions. The Lewis adducts CH3 N3 â AsF5 and CF3 N3 â AsF5 were also prepared and characterized by low-temperature NMR and Raman spectroscopy, and also by X-ray structure determination for CH3 N3 â AsF5 . Electronic structure calculations were performed to provide additional insights. Attempted electrophilic amination of aromatics such as benzene and toluene with methyl- and trifluoromethylamino diazonium ions were unsuccessful.
RESUMO
A novel amine-assisted route for low temperature homogeneous hydrogenation of CO to methanol is described. The reaction proceeds through the formation of formamide intermediates. The first amine carbonylation part is catalyzed by K3PO4. Subsequently, the formamides are hydrogenated in situ to methanol in the presence of a commercially available ruthenium pincer complex as a catalyst. Under optimized reaction conditions, CO (up to 10 bar) was directly converted to methanol in high yield and selectivity in the presence of H2 (70 bar) and diethylenetriamine. A maximum TON of 539 was achieved using the catalyst Ru-Macho-BH. The high yield, selectivity, and TONs obtained for methanol production at low reaction temperature (145 °C) could make this process an attractive alternative over the traditional high temperature heterogeneous catalysis.
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Amine-assisted homogeneous hydrogenation of CO2 to methanol is one of the most effective approaches to integrate CO2 capture with its subsequent conversion to CH3OH. The hydrogenation typically proceeds in two steps. In the first step the amine is formylated via an in situ formed alkylammonium formate salt (with consumption of 1 equiv of H2). In the second step the generated formamide is further hydrogenated with 2 more equiv of H2 to CH3OH while regenerating the amine. In the present study, we investigated the effect of molecular structure of the ruthenium pincer catalysts and the amines that are critical for a high methanol yield. Surprisingly, despite the high reactivity of several Ru pincer complexes [RuHClPNP R(CO)] (R = Ph/ i-Pr/Cy/ t-Bu) for both amine formylation and formamide hydrogenation, only catalyst Ru-Macho (R = Ph) provided a high methanol yield after both steps were performed simultaneously in one pot. Among various amines, only (di/poly)amines were effective in assisting Ru-Macho for methanol formation. A catalyst deactivation pathway was identified, involving the formation of ruthenium biscarbonyl monohydride cationic complexes [RuHPNP R(CO)2]+, whose structures were unambiguously characterized and whose reactivities were studied. These reactivities were found to be ligand-dependent, and a trend could be established. With Ru-Macho, the biscarbonyl species could be converted back to the active species through CO dissociation under the reaction conditions. The Ru-Macho biscarbonyl complex was therefore able to catalyze the hydrogenation of in situ formed formamides to methanol. Complex Ru-Macho-BH was also highly effective for this conversion and remained active even after 10 days of continuous reaction, achieving a maximum turnover number (TON) of 9900.
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Facile synthesis of a new series of 2,2'-bis(trifluoroacetyl) azoxybenzene derivatives and trifluoromethylated benzo[c]isoxazoline systems, along with trifluoroacetyl nitrosobenzene derivatives was achieved by solvent controlled photolysis of appropriate 2-nitrobenzyl alcohols. Corresponding photoactive 2-nitrobenzyl chromophore plays a distinct role in this photosynthetic process, while, quite unprecedented, pertinent fluoromethyl substitution leads to high value fluoromethylated products, whose direct access is not feasible by common synthetic protocols. The significance of fluorine and fluoroalkyl substitution and its prominent biological effects makes this new photochemical approach an important discovery in synthetic methodology. Plausible mechanistic pathways involved in the formation of the products during steady-state photolysis are further established by picosecond laser flash photolysis experiments.
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A variety of long-lived carbocations containing the p-(pentafluorosulfanyl)phenyl and m-(pentafluorosulfanyl)phenyl groups have been characterized by low-temperature NMR spectroscopy. In the case of potential nonclassical carbocations substituted with the p-(pentafluorosulfanyl)phenyl substituent, deviations from linearity when the Hammett parameter (σC+) is plotted versus 13C NMR shifts of the carbocationic center were observed. Plotting the experimentally derived 13C NMR shifts versus σC+ or σ+ of classical 4-phenyl-X substituted carbocations also provides a means to accurately back-calculate the σ+ and σC+ parameters of the -SF5 substituent.
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The structures of the elusive cyclobutane dication, (CH2)4 2+, were investigated at the MP2/cc-pVTZ and CCSD(T)/cc-pVTZ levels. Calculations show that the two-electron four-center (2e-4c) bonded structure 1 involving four carbon atoms is a minimum. The structure contains formally two tetracoordinate and two pentacoordinate carbons. The non-classical σ-delocalized structure can be considered as a prototype for a 2e-4c Woodward-Hoffmann frozen transition state. The planar rectangular shaped structure 2 with a 2e-4c bond was found not to be a minimum.
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Herein we report an efficient and recyclable system for tandem CO2 capture and hydrogenation to methanol. After capture in an aqueous amine solution, CO2 is hydrogenated in high yield to CH3OH (>90%) in a biphasic 2-MTHF/water system, which also allows for easy separation and recycling of the amine and catalyst for multiple reaction cycles. Between cycles, the produced methanol can be conveniently removed in vacuo. Employing this strategy, catalyst Ru-MACHO-BH and polyamine PEHA were recycled three times with 87% of the methanol producibility of the first cycle retained, along with 95% of catalyst activity after four cycles. CO2 from dilute sources such as air can also be converted to CH3OH using this route. We postulate that the CO2 capture and hydrogenation to methanol system presented here could be an important step toward the implementation of the carbon neutral methanol economy concept.
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A highly efficient recyclable system for capture and subsequent conversion of CO2 to formate salts is reported that utilizes aqueous inorganic hydroxide solutions for CO2 capture along with homogeneous pincer catalysts for hydrogenation. The produced aqueous solutions of formate salts are directly utilized, without any purification, in a direct formate fuel cell to produce electricity and regenerate the hydroxide base, achieving an overall carbon-neutral cycle. The catalysts and organic solvent are recycled by employing a biphasic solvent system (2-MTHF/H2O) with no significant decrease in turnover frequency (TOF) over five cycles. Among different hydroxides, NaOH and KOH performed best in tandem CO2 capture and conversion due to their rapid rate of capture, high formate conversion yield, and high catalytic TOF to their corresponding formate salts. Among various catalysts, Ru- and Fe-based PNP complexes were the most active for hydrogenation. The extremely low vapor pressure, nontoxic nature, easy regenerability, and high reactivity of NaOH/KOH toward CO2 make them ideal for scrubbing CO2 even from low-concentration sources-such as ambient air-and converting it to value-added products.
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Formation of methanol and hydrocarbon derivatives from CO2 and H2, their simplest molecular building blocks, under biocompatible conditions is proposed. Alternate panspermia of similar extraterrestrially formed and observed hydrocarbons to earth is also discussed. The simple molecular building blocks derived from CO2 and H2 are carbon sources in the initial stage of biological evolution of cells leading to life's origin.
Assuntos
Evolução Biológica , Dióxido de Carbono/química , Carbono/química , Metanol/químicaRESUMO
Methane was converted to light olefins (ethene and propene) or higher hydrocarbons in a continuous flow reactor below 375 °C over H-SAPO-34 catalyst via an in situ halogenation (chlorination/bromination) protocol. The reaction conditions can be efficiently tuned toward selective monohalogenation of methane to methyl halides or their in situ oligomerization to higher hydrocarbons. The presence of C5+ hydrocarbons in the reaction products clearly indicates that by using a properly engineered catalyst under optimized reaction conditions, hydrocarbons in the gasoline range can be produced. This approach has significant potential for feasible application in natural gas refining to gasoline and materials under moderate operational conditions.
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A novel hydrogen storage system based on the hydrogen release from catalytic dehydrogenative coupling of methanol and 1,2-diamine is demonstrated. The products of this reaction, N-formamide and N,N'-diformamide, are hydrogenated back to the free amine and methanol by a simple hydrogen pressure swing. Thus, an efficient one-pot hydrogen carrier system has been developed. The H2 generating step can be termed as "amine reforming of methanol" in analogy to the traditional steam reforming. It acts as a clean source of hydrogen without concurrent production of CO2 (unlike steam reforming) or CO (by complete methanol dehydrogenation). Therefore, a carbon neutral cycle is essentially achieved where no carbon capture is necessary as the carbon is trapped in the form of formamide (or urea in the case of primary amine). In theory, a hydrogen storage capacity as high as 6.6 wt % is achievable. Dehydrogenative coupling and the subsequent amide hydrogenation proceed with good yields (90% and >95% respectively, with methanol and N,N'-dimethylethylenediamine as dehydrogenative coupling partners).
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Astrophysical observations show similarity of observed abiological "organics"-i.e., hydrocarbons, their derivatives, and ions (carbocations and carbanions)-with studied terrestrial chemistry. Their formation pathways, their related extraterrestrial hydrocarbon chemistry originating from carbon and other elements after the Big Bang, their parent hydrocarbon and derivative (methane and methanol, respectively), and transportation of derived building blocks of life by meteorites or comets to planet Earth are discussed in this Perspective. Their subsequent evolution on Earth under favorable "Goldilocks" conditions led to more complex molecules and biological systems, and eventually to humans. The relevance and significance of extraterrestrial hydrocarbon chemistry to the limits of science in relation to the physical aspects of evolution on our planet Earth are also discussed.
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A highly efficient homogeneous catalyst system for the production of CH3OH from CO2 using pentaethylenehexamine and Ru-Macho-BH (1) at 125-165 °C in an ethereal solvent has been developed (initial turnover frequency = 70 h(-1) at 145 °C). Ease of separation of CH3OH is demonstrated by simple distillation from the reaction mixture. The robustness of the catalytic system was shown by recycling the catalyst over five runs without significant loss of activity (turnover number > 2000). Various sources of CO2 can be used for this reaction including air, despite its low CO2 concentration (400 ppm). For the first time, we have demonstrated that CO2 captured from air can be directly converted to CH3OH in 79% yield using a homogeneous catalytic system.
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Astrophysically observed extraterrestrial molecular matter contains, besides hydrogen and water, methane and methanol as the most abundant species. Feasible pathways and chemical aspects of their formation as well as of derived hydrocarbon homologues and their ions (carbocations and carbanions) are discussed on the basis of observed similarities with our studied terrestrial chemistry. The preferred pathway for converting extraterrestrial methane according to Ali et al. is based on CH5(+) and Olah's related nonclassical carbonium ion chemistry. On the basis of the observed higher reactivity of methanol compared with methane in various chemical reactions, a feasible new pathway is proposed for the conversion of extraterrestrial methanol to hydrocarbons, their derivatives, and carbocations together with a possible connection with methonium ion-based chemistry.
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The rearrangement pathways of the equilibrating tertiary carbocations, 2,3-dimethyl-2-butyl cation (C6H13(+), 1), 2,3,3-trimethyl-2-butyl cation (C7H15(+), 5) and 2,3-dimethyl-2-pentyl cation (C7H15(+), 8 and 9) were investigated using the ab initio/GIAO-CCSD(T) (13)C NMR method. Comparing the calculated and experimental (13)C NMR chemical shifts of a series of carbocations indicates that excellent prediction of δ(13)C could be achieved through scaling. In the case of symmetrical equilibrating cations (1 and 5) the Wagner-Meerwein 1,2-hydride and 1,2-methide shifts, respectively, produce the same structure. This indicates that the overall (13)C NMR chemical shifts are conserved and independent of temperature. However, in the case of unsymmetrical equilibrating cations (8 and 9) the Wagner-Meerwein shift produces different tertiary structures, which have slightly different thermodynamic stabilities and, thus, different spectra. At the MP4(SDTQ)/cc-pVTZ//MP2/cc-pVTZ + ZPE level structure 8 is only 90 calories/mol more stable than structure 9. Based on computed (13)C NMR chemical shift calculations, mole fractions of these isomers were determined by assuming the observed chemical shifts are due to the weighted average of the chemical shifts of the static ions.
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Phosphazenes of vinyldiazocarbonyl compounds having cis stereochemistry of the functional groups on the vinyl bond readily produce pyridazines by a diaza-Wittig process, whereas their counterparts with trans configuration remain intact under similar reaction conditions. Upon UV irradiation trans-phosphazenes furnish pyridazines through a tandem trans-to-cis isomerization followed by intramolecular cyclization. At elevated temperatures trans-(triphenyl)phosphazenes dissociate to give the initial vinyldiazo compounds, which produce pyrazoles in high yields. The first theoretical study on the mechanism of the diaza-Wittig process by DFT calculations at the M06-2X/6-31G(d) level of theory suggest that for the cis-phosphazenes a rapid tandem [2+2] cycloaddition/cycloelimination process with low energy barriers is preferred over trans isomers.