Front Cover: Preparation and Characterization of Protonated Fumaric Acid (Z. Anorg. Allg. Chem. 7/2020)

Bayer, Marie C.; Jessen, Christoph; Kornath, Andreas

doi:10.1002/zaac.202070071

Cited by 3 publications

(4 citation statements)

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“…The fact that this frequency in ( 1 ) and ( 2 ) appears lower than expected for this group can be explained by the above‐mentioned hydrogen bond between the cations. The ν(CF) vibration occurs at about 1240 cm −1 in ( 1 ) and at 1235 cm −1 in ( 2 ), which is in accordance with reported literature data [20,21] . Due to the protonation, the CO stretching vibration of the alcohol group is red‐shifted compared to unprotonated primary alcohols [22] .…”

Section: Resultssupporting

confidence: 88%

Ring Opening and Closure Reactions of β‐Propiolactone in the Superacids HF/MF₅ (M=Sb, As)

2021

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Transformations of β‐propiolactone in the binary superacidic systems HF/MF5 (M=Sb, As) were investigated at different temperatures. Salts of monoprotonated 3‐hydroxypropanoyl fluoride [H2O(CH2)2C(O)F][SbF6] (1) and [H2O(CH2)2C(O)F][AsF6] (2) were obtained by performing the reactions at temperatures lower than −40 °C. In contrast, temperatures higher than −40 °C yield the respective salts [C9H15O6][SbF6]3 (3) and [C9H15O6][AsF6]3 (4) containing a cyclic trication. The protonated species of β‐propiolactone was not observed. All salts were characterized by low temperature Raman and IR spectroscopy. In addition, single‐crystal X‐ray analyses were performed for (1) and (3). For both cations the existence of a cationic acyl species as a reactive intermediate in the form of [HO(CH2)2CO][MF6] is assumed. The formation of the acyl cation, based on protonated β‐propiolactone, was investigated by quantum chemical calculations on the MP2/aug‐cc‐pVTZ level of theory.

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Section: Resultssupporting

confidence: 88%

Ring Opening and Closure Reactions of β‐Propiolactone in the Superacids HF/MF₅ (M=Sb, As)

2021

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“…A similar structure of polycationic chains with twofold hemiprotonated molecules is observed in monoprotonated p-benzoquinone and fumaric acid. [10,11] When formally monoprotonated acetylenedicarboxylic acid ( 4) is compared to monoprotonated oxalic acid, there is an interesting difference in the crystal packing. Oxalic acid shows a clear monoprotonation in its crystal structure, even though it also builds cationic chains via hydrogen bonds (Figure 4).…”

Section: Crystal Structure Of Monoprotonated Acetylenedicarboxylic Ac...mentioning

confidence: 99%

“…This approach has already been successfully applied to simulate hydrogen bonding and is in good accordance with the data from the crystal structures (3) and ( 4). [11,18] Comparing the crystal and calculated gas phase structures, it stands out that the carbon scaffold is not changed significantly by the degree of protonation. Therefore, it is interesting to compare the protonated species of this work with anionic species of acetylenedicarboxylic acid from the literature.…”

Section: Quantum Chemical Calculationsmentioning

confidence: 99%

Syntheses and Structures of Protonated Acetylenedicarboxylic Acid

Jessen

Kornath

2022

Eur J Inorg Chem

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Acetylenedicarboxylic acid (C 4 H 2 O 4 ) was protonated in the binary superacidic systems HF/MF 5 (M = As, Sb). Depending on the stoichiometric ratio of Lewis acid and acetylenedicarboxylic acid mono-and diprotonated acetylenedicarboxylic acid was obtained. The salts of diprotonated acetylenedicarboxylic acid were characterized by vibrational spectroscopy and in case of [C 4 H 4 O 4 ][SbF 6 ] 2 by a single-crystal X-ray structure analysis. The salt crystallizes in the monoclinic space group C2/c with four formula units per unit cell. Furthermore, salts of monoprotonated acetylenedicarboxylic acid were synthesized and characterized by single-crystal X-ray structure analysis. The salts [C 4 H 3 O 4 ][AsF 6 ] and [C 4 H 3 O 4 ][SbF 6 ] crystallize in the monoclinic space group C2/c with four formula units per unit cell. The monoprotonation is better described as a twofold hemiprotonation of acetylenedicarboxylic acid. The experimental results are discussed together with quantum chemical calculations.

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“…This range for ν(CO) is typical for acyl fluoride groups. [20,21] At 1157 cm À 1 in both Raman spectra and at 1165 (1) and 1155 cm À 1 (2) in the IR spectra, the corresponding ν(CF) vibrations are observed. For the NH 3 group three NH stretching vibrations are expected.…”

Section: Monoprotonated 3-aminopropanoyl Fluoridementioning

confidence: 99%

Ring Opening Reactions of β‐Propiolactam in Superacidic Media

Beck

Rück

Pietsch

et al. 2022

Chemistry A European J

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The reaction of β-propiolactam in the superacidic systems HF/MF 5 (M = Sb, As) led to the formation of monoprotonated 3-aminopropanoyl fluoride in the form of [C(O)F(CH 2 ) 2 NH 3 ][SbF 6 ] and [C(O)F(CH 2 ) 2 NH 3 ][AsF 6 ]. In the presence of traces of water, the diprotonated species β-alanine [C(OH) 2 (CH 2 ) 2 NH 3 ][AsF 6 ] 2 was synthesized for the first time. All salts were characterized by low-temperature infrared and Raman spectroscopy. Additionally, single-crystal X-ray analyses were conducted in the case of [C(O)F(CH 2 ) 2 NH 3 ][SbF 6 ] and [C(OH) 2 (CH 2 ) 2 NH 3 ][AsF 6 ] 2 . By using SO 2 instead of HF as the solvent, the salt [C(OH) 2 (CH 2 ) 2 NHSO][SbF 6] 2 was obtained, and single-crystal X-ray analysis of this salt containing a thionylimide moiety was conducted. For the formation of these open-chain compounds, an acyl cationic species as intermediate is assumed, which is formed from N-protonated βpropiolactam. Quantum chemical calculations at the B3LYP/ aug-cc-pVTZ and MP2/aug-cc-pVTZ levels of theory were carried out to gain a better understanding of the formation and the structural properties of protonated β-propiolactam.

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Front Cover: Preparation and Characterization of Protonated Fumaric Acid (Z. Anorg. Allg. Chem. 7/2020)

Cited by 3 publications

References 0 publications

Ring Opening and Closure Reactions of β‐Propiolactone in the Superacids HF/MF₅ (M=Sb, As)

Ring Opening and Closure Reactions of β‐Propiolactone in the Superacids HF/MF₅ (M=Sb, As)

Syntheses and Structures of Protonated Acetylenedicarboxylic Acid

Ring Opening Reactions of β‐Propiolactam in Superacidic Media

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Front Cover: Preparation and Characterization of Protonated Fumaric Acid (Z. Anorg. Allg. Chem. 7/2020)

Cited by 3 publications

References 0 publications

Ring Opening and Closure Reactions of β‐Propiolactone in the Superacids HF/MF5 (M=Sb, As)

Ring Opening and Closure Reactions of β‐Propiolactone in the Superacids HF/MF5 (M=Sb, As)

Syntheses and Structures of Protonated Acetylenedicarboxylic Acid

Ring Opening Reactions of β‐Propiolactam in Superacidic Media

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Ring Opening and Closure Reactions of β‐Propiolactone in the Superacids HF/MF₅ (M=Sb, As)

Ring Opening and Closure Reactions of β‐Propiolactone in the Superacids HF/MF₅ (M=Sb, As)