Gas phase observation and microwave spectroscopic characterization of formic sulfuric anhydride

Mackenzie, Rebecca B.; Dewberry, Christopher T.; Leopold, K. R.

doi:10.1126/science.aaa9704

Cited by 51 publications

(67 citation statements)

References 30 publications

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“…Considering that K 2 S 2 O 8 was used as oxidant, the sulfo group was regarded to come from sulfur trioxide, and the carboxyl group (formate) should be generated by the decarbonylation or oxidation of HMF to AFI or MA. Sulfur trioxide and formic acid form mixed sulfonic–formic anhydride (Scheme ) . Indeed, formic acid was detected in the reaction solution (Figure S4).…”

Section: Resultssupporting

confidence: 57%

“…Sulfur trioxide and formic acid form mixed sulfonic-formica nhydride (Scheme 3). [32] Indeed, formic acid was detected in the reactions olution (Figure S4). The decrease in the pH of the reaction solution from 7.3 to 0.1 after the reaction indicated the formation of acids, such as H 2 SO 4 generated from the reaction of SO 3 with water and formic acid from oxidation of the aldehyde group in DFF (Table S1).…”

Section: Resultsmentioning

confidence: 97%

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One‐Pot Synthesis of Renewable Phthalic Anhydride from 5‐Hydroxymethfurfural by using MoO₃/Cu(NO₃)₂ as Catalyst

et al. 2019

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Herein, a synthetic pathway to renewable phthalic anhydride (PA) from 5‐hydroxymethfurfural (HMF) in one pot is reported. The commonly available catalysts MoO3 and Cu(NO3)2 play a crucial role in integrating the multiple steps of the reaction, namely decarbonylation of HMF to active furyl intermediate (AFI), oxidation of HMF to maleic anhydride (MA), Diels–Alder cycloaddition of AFI and MA, and subsequent dehydration, in one pot. Under mild reaction conditions, a 63.2 % yield of PA is obtained from HMF. Compared with the currently reported route to renewable PA based on the Diels–Alder cycloaddition of biomass‐derived MA and furan, this convenient one‐pot synthesis represents a great improvement in efficiency.

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Section: Resultssupporting

confidence: 57%

Section: Resultsmentioning

confidence: 97%

One‐Pot Synthesis of Renewable Phthalic Anhydride from 5‐Hydroxymethfurfural by using MoO₃/Cu(NO₃)₂ as Catalyst

et al. 2019

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“…Considering the importance of SA in particle formation, this reaction, in part, explains the acceleration effect of organic acids on PM formation. Recently, another gas‐phase reaction mechanism of organic acids and SO 3 was proposed as feasible in atmosphere . In this second mechanism, a facile [π2+π2+σ2] cycloaddition between organic acids and SO 3 was observed, leading to the formation of sulfuric‐carboxylic anhydrides.…”

Section: Figurementioning

confidence: 99%

“…Although both of the above mechanisms for the reaction between organic acids and SO 3 can explain the enhanced particle formation to some extent, they are still limited to the gas phase. In the atmosphere, liquid phases are abundant in the form of clouds, aerosols, or sea‐salt particles.…”

Section: Figurementioning

confidence: 99%

Mechanistic Insight into the Reaction of Organic Acids with SO₃ at the Air–Water Interface

Zhong

Li²,

Kumar

et al. 2019

Angew Chem Int Ed

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The gas‐phase reaction of organic acids with SO3 has been recognized as essential in promoting aerosol‐particle formation. However, at the air–water interface, this reaction is much less understood. We performed systematic Born–Oppenheimer molecular dynamics (BOMD) simulations to study the reaction of various organic acids with SO3 on a water droplet. The results show that with the involvement of interfacial water molecules, organic acids can react with SO3 and form the ion pair of sulfuric‐carboxylic anhydride and hydronium. This mechanism is in contrast to the gas‐phase reaction mechanisms in which the organic acid either serves as a catalyst for the reaction between SO3 and H2O or reacts with SO3 directly. The distinct reaction at the water surface has important atmospheric implications, for example, promoting water condensation, uptaking atmospheric condesation species, and incorporating “SO42−” into organic species in aerosol particles. Therefore, this reaction, typically occurring within a few picoseconds, provides another pathway towards aerosol formation.

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“… The reaction occurs spontaneously and completes within a time scale of ∼100 fs . It is proposed that the external OH − ‐induced concerted proton transfer on the Al 3+ coordinated waters and the solvent waters can be treated as downhill barrierless reactions …”

Section: Resultsmentioning

confidence: 99%

Density functional theory studies on the external OH⁻‐induced barrierless proton dissociation mechanism for the forced hydrolysis reaction of Al³⁺(aq)

Dong

Shi

Zhang

et al. 2018

Int J of Quantum Chemistry

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The forced hydrolysis reaction of aqueous aluminum ion (Al 3+ ) is of critical importance in Al chemistry, but its microscopic mechanism has long been neglected. Herein, density functional calculations reveal an external OH − -induced barrierless proton dissociation mechanism for the forced hydrolysis of Al 3+ (aq). Dynamic reaction pathway modeling results show that the barrierless deprotonations induced by the second-or third-shell external OH − proceed via the concerted proton transfer through H-bond wires connected to the coordinated waters, and the inducing ability of the external OH − decreases with increasing hydration layers between Al(H 2 O) 6 3+ and the external OH − . The OH − -induced forced hydrolysis mechanism of Al 3+ (aq) is quite different from its self-hydrolysis mechanism without OH − . The inducing ability is a unique characteristic of OH − , rather than other anions such as F − or Cl − .aluminium ion, barrierless proton dissociation, density functional theory, forced hydrolysis,The hydrolysis chemistry of aluminum (Al) is central to environmental science, human health and industry activities. [1][2][3] Extensive efforts have been devoted to exploring the self and forced hydrolysis reactions of Al 3+ (aq) in aqueous solution that form various monomeric and polymeric hydrolytic Al species. [4] Unlike the self-hydrolysis of Al 3+ (aq) in acidic solutions whose detailed reaction steps have been carefully studied using both experimental [5,6] and theoretical [7][8][9][10][11] methods, the microscopic reaction kinetics for the forced hydrolysis of Al 3+ (aq) under elevated pH conditions such as base titration is rarely considered, and the role of hydroxyl in the formation mechanisms of the hydrolytic Al species remains poorly understood. This has hindered the precision studies of the hydrolysis-polymerization mechanisms of Al species.Conventionally, the self-hydrolysis of Al 3+ (aq) is viewed as the spontaneous proton removal on Al 3+ inner-shell coordinated waters with the assistance of adjacent solvent water molecules, [12] while the forced hydrolysis of Al 3+ (aq) involves the participation of external OH − . The firstorder forced hydrolysis of Al 3+ (aq), which acts as the first reaction step in forming polymeric hydroxyl Al species upon base titration, is usually expressed as: [13,14] Al 3 + + OH − ! AlðOHÞ 2 +AlðH 2 OÞ 6 3 + + OH − ! AlðOHÞðH 2 OÞ 5 2 + + H 2 O:In aqueous solution, the Al 3+ ion exists mainly in the hydrated form of Al(H 2 O) 6 3+ rather than the naked Al 3+ , thus, Equation (2) is more suitable to describe the reaction in aqueous solution. The reaction may proceed via the pathway that a proton on an Al(H 2 O) 6 3+ inner-shell coordinated water dissociates and moves into OH − , or in other words, the external OH − captures the proton. Herein, this possible reaction pathway is modeled using the density functional theory-quantum chemical cluster model (DFT-CM) method, [15,16] in order to elucidate the molecular mechanism of the forced hydrolysis reaction of Al 3+ (aq) in aqueou...

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Gas phase observation and microwave spectroscopic characterization of formic sulfuric anhydride

Cited by 51 publications

References 30 publications

One‐Pot Synthesis of Renewable Phthalic Anhydride from 5‐Hydroxymethfurfural by using MoO₃/Cu(NO₃)₂ as Catalyst

One‐Pot Synthesis of Renewable Phthalic Anhydride from 5‐Hydroxymethfurfural by using MoO₃/Cu(NO₃)₂ as Catalyst

Mechanistic Insight into the Reaction of Organic Acids with SO₃ at the Air–Water Interface

Density functional theory studies on the external OH⁻‐induced barrierless proton dissociation mechanism for the forced hydrolysis reaction of Al³⁺(aq)

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Gas phase observation and microwave spectroscopic characterization of formic sulfuric anhydride

Cited by 51 publications

References 30 publications

One‐Pot Synthesis of Renewable Phthalic Anhydride from 5‐Hydroxymethfurfural by using MoO3/Cu(NO3)2 as Catalyst

One‐Pot Synthesis of Renewable Phthalic Anhydride from 5‐Hydroxymethfurfural by using MoO3/Cu(NO3)2 as Catalyst

Mechanistic Insight into the Reaction of Organic Acids with SO3 at the Air–Water Interface

Density functional theory studies on the external OH−‐induced barrierless proton dissociation mechanism for the forced hydrolysis reaction of Al3+(aq)

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One‐Pot Synthesis of Renewable Phthalic Anhydride from 5‐Hydroxymethfurfural by using MoO₃/Cu(NO₃)₂ as Catalyst

One‐Pot Synthesis of Renewable Phthalic Anhydride from 5‐Hydroxymethfurfural by using MoO₃/Cu(NO₃)₂ as Catalyst

Mechanistic Insight into the Reaction of Organic Acids with SO₃ at the Air–Water Interface

Density functional theory studies on the external OH⁻‐induced barrierless proton dissociation mechanism for the forced hydrolysis reaction of Al³⁺(aq)