Trihydroxycarbenium Hexafluorometalates: Salts of Protonated Carbonic Acid

Minkwitz, R.; Schneider, Stefan

doi:10.1002/(sici)1521-3773(19990301)38:5<714::aid-anie714>3.3.co;2-b

Cited by 15 publications

(34 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The hydrogen‐bonded CH 3 + ⋅Ar structure has a far lower binding energy (3.6 kJ mol −1 ). In contrast, the IR spectra and calculations for C(OH) 3 + ⋅Ar confirm previous conclusions18, 19 that the charge in C(OH) 3 + is largely delocalized, and as a result, the hydrogen‐bonded complex is more stable (6.6 kJ mol −1 ) than the C‐bound one (0.8 kJ mol −1 ).…”

supporting

confidence: 84%

“…In the NMR, IR, Raman, and X‐ray crystallography spectra of C(OH) 3 + in superacid solutions or corresponding salts only the anti isomer was observed 18. 19 Finally, a fourth nonplanar [C,H 3 ,O 3 ] + isomer can be generated by protonation of H 2 CO 3 at a hydroxyl group ( 3 , C 1 , E rel =118 kJ mol −1 ), leading to a hitherto undetected complex of H 2 O and OCOH + 14 with a binding energy of 105 kJ mol −1 .…”

mentioning

confidence: 99%

See 1 more Smart Citation

IR Spectra of Protonated Carbonic Acid and Its Isomeric H₃O⁺⋅CO₂ Complex

2007

View full text Add to dashboard Cite

Die Autoren möchten eine Bemerkung in der Einführung dieser Zuschrift korrigieren. Die Aussage "There have been several unsuccessful attempts to generate and characterize gas-phase H 2 CO 3 by heating solid H 2 CO 3 [3] or NH 4 HCO 3 [12] " ist irreführend und muss ersetzt werden durch "Although there have been several successful attempts to generate and identify gas-phase H 2 CO 3 by heating solid H 2 CO 3 [3] or NH 4 HCO 3 , [12] there is still a lack of detailed experimental information on its structural, spectroscopic, and thermochemical properties."

show abstract

supporting

confidence: 84%

mentioning

confidence: 99%

IR Spectra of Protonated Carbonic Acid and Its Isomeric H₃O⁺⋅CO₂ Complex

2007

View full text Add to dashboard Cite

show abstract

“…Mass spectrometry studies, along with gas‐phase calculations, have suggested that formaldehyde and acetaldehyde form hydrogen‐bridged dimers, (RCHO) 2 H + (R=H or CH 3 ) . Attempts to synthesize protonated formaldehyde in the solid state have been unsuccessful and instead a [H 2 C=O−CH 2 OH] + salt was obtained in HF/SbF 5 at −78 °C …”

Section: Methodsmentioning

confidence: 99%

Solid‐State Structure of Protonated Ketones and Aldehydes

2017

View full text Add to dashboard Cite

Protonated carbonyl compounds have been invoked as intermediates in many acid-catalyzed organic reactions.T o gain key structural and electronic data about such intermediates,o xonium salts derived from five representative examples of ketones and aldehydes are synthesized in the solid state,and characterized by X-rayc rystallography and Raman spectroscopyfor the first time.DFT calculations were carried out on the cations in the gas phase.Whereas an equimolar reaction of the carbonyl compounds,a cetone,c yclopentanone,a damantanone,a nd acetaldehyde,w ith SbF 5 in anhydrous HF yielded mononuclear oxonium cations,t he same stoichiometry in areaction with benzaldehyde resulted in formation of ahemiprotonated, hydrogen-bridged dimeric cation. Hemiprotonated acetaldehyde was obtained when a2:1 ratio of aldehyde and SbF 5 was used. Experimental and NBO analyses quantify the significant increase in electrophilicity of the oxonium cations compared to that of the parent ketones/aldehydes.In targeted reactions,s alts of protonated ketones and aldehydes were isolated using stoichiometric amounts of Scheme 1. Resonance structures for protonated ketones.

show abstract

“…Im Fall der Supersäure HF/SbF 5 wurden in SO 2 als Lösungsmittel nur marginale Unterschiede in der Protonenübertragungstendenz, d. h. den −H 0 ‐Werten beobachtet 2. Schwefeldioxid hat demzufolge keinen Einfluss auf Reaktionen in supersauren Systemen und wurde daher als Lösungsmittel für aus diesen Medien isolierte Salze verwendet 3–5 …”

Section: Schwingungsfrequenzen [Cm−1] Des Feststoffs[a]unclassified