Methanediol decomposition mechanisms: A study considering various ab initio approaches

Böhm, Stanislav; Antipova, Diana; Kuthan, J.

doi:10.1002/(sici)1097-461x(1996)58:1<47::aid-qua6>3.0.co;2-y

Cited by 17 publications

(10 citation statements)

References 13 publications

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“…Comparison of our result with the value obtained with the ADF package by using a large basis set 38 and the BLYP functional confirms the good accuracy of the pseudopotential approach. However, the reaction energy we obtained is substantially smaller than the values of MP2 and MP4 calculations. ,, This is reason for some concern. Previous experience with related reactions 19,20 suggests that BLYP has a tendency to underestimate the energy gained by converting a bond of high bond order, such as a carbonyl bond, to two bonds of lower bond order.…”

Section: Gas-phase Structure and Energeticscontrasting

confidence: 53%

Ab Initio Molecular Dynamics Study of the Reaction of Water with Formaldehyde in Sulfuric Acid Solution

Sprik

Meijer

1998

J. Am. Chem. Soc.

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Ab initio molecular dynamics methods have been used to study the reaction mechanism of acid-catalyzed addition of water to formaldehyde in a model system of an aqueous solution of sulfuric acid. Using the method of constraints we find that an H2O molecule can be added to formaldehyde by a controlled transfer of a catalytic proton from a hydronium ion in acid solution to the carbonyl oxygen. The formation of the CO bond between the carbonyl carbon and the water oxygen occurs at a stage midway in the proton transfer process. The process can be reversed by removing the H+ from the protonated product diol, leading to CO bond breaking at approximately the same stage of proton transfer. This suggests that the kinetics of the acid-catalyzed reaction is governed by a concerted protonation and addition.

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Section: Gas-phase Structure and Energeticscontrasting

confidence: 53%

Ab Initio Molecular Dynamics Study of the Reaction of Water with Formaldehyde in Sulfuric Acid Solution

Sprik

Meijer

1998

J. Am. Chem. Soc.

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“…Prior theoretical work has been devoted to exploring the stability and catalytic decomposition dynamics of 1 ( 8 – 10 , 25 – 29 ). Kent et al.…”

Section: Discussionmentioning

confidence: 99%

“…challenged this conclusion and computationally uncovered that tunneling enhances the decomposition rate by one to nine orders of magnitude at atmospherically relevant temperatures of 200 K to 300 K ( 27 ). Tropospheric trace components such as water (H 2 O) and formic acid (HCOOH) might lower the dehydration barrier by 87 kJ ⋅ mol −1 to 155 kJ ⋅ mol −1 ( 8 , 25 , 27 ). Furthermore, 1 may even catalyze its own decomposition at temperatures below 280 K ( 27 ).…”

Section: Discussionmentioning

confidence: 99%

“…Gas-phase electronic structure calculations predict that two conformers of methanediol [CH 2 (OH) 2 ] ( 1′ , 1″ ) are thermodynamically favorable compared to the well-known methyl peroxide isomer (CH 3 OOH, 2 ) by 267 kJ ⋅ mol −1 and 257 kJ ⋅ mol −1 , respectively; these conformers are also thermodynamically and kinetically stable toward unimolecular decomposition via dehydration to the formaldehyde–water complex ( 3 ), as the 1′ to 3 and 1″ to 3 reactions are endoergic by 21 and 11 kJ ⋅ mol −1 and have barriers of 181 and 191 kJ ⋅ mol −1 , respectively ( 8 – 11 ) ( Fig. 1 ).…”

mentioning

confidence: 99%

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Synthesis of methanediol [CH ₂ (OH) ₂ ]: The simplest geminal diol

Zhu

Kleimeier

Turner

et al. 2021

Proc. Natl. Acad. Sci. U.S.A.

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Geminal diols—organic molecules carrying two hydroxyl groups at the same carbon atom—have been recognized as key reactive intermediates by the physical (organic) chemistry and atmospheric science communities as fundamental transients in the aerosol cycle and in the atmospheric ozonolysis reaction sequence. Anticipating short lifetimes and their tendency to fragment to water plus the aldehyde or ketone, free geminal diols represent one of the most elusive classes of organic reactive intermediates. Here, we afford an exceptional glance into the preparation of the previously elusive methanediol [CH2(OH)2] transient—the simplest geminal diol—via energetic processing of low-temperature methanol–oxygen ices. Methanediol was identified in the gas phase upon sublimation via isomer-selective photoionization reflectron time-of-flight mass spectrometry combined with isotopic substitution studies. Electronic structure calculations reveal that methanediol is formed via excited state dynamics through insertion of electronically excited atomic oxygen into a carbon–hydrogen bond of the methyl group of methanol followed by stabilization in the icy matrix. The first preparation and detection of methanediol demonstrates its gas-phase stability as supported by a significant barrier hindering unimolecular decomposition to formaldehyde and water. These findings advance our perception of the fundamental chemistry and chemical bonding of geminal diols and signify their role as an efficient sink of aldehydes and ketones in atmospheric environments eventually coupling the atmospheric chemistry of geminal diols and Criegee intermediates.

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“…and formaldehyde were studied theoretically [1][2][3][4][5][6][7][8][9][10][11]. In the hydration of formaldehyde (reaction (1) in Scheme 1), it was found that the potential energy barrier can be significantly lowered due to the catalytic effect of water [1][2][3][4][5][6]. There are similar findings that water molecules play a catalytic role in amination reactions of ammonia (NH 3 ) and methylamine (CH 3 NH 2 ) with formaldehyde [7][8][9] (reaction (2) in Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

A computational study on the reaction mechanism of neutral phenol with formaldehyde in aqueous solution

Cao

et al. 2016

Progress in Reaction Kinetics and Mechanism

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The reaction mechanism of neutral phenol with formaldehyde in aqueous solution was studied theoretically by using the GGA-PW91/DNP+COSMO method. In previous studies, it was found that the water molecules can mediate proton transfer from nitrogen to oxygen, but the results of this study show that water molecules can also catalyse proton transfer from carbon to oxygen. With the mediation of water, the energy barriers were greatly lowered. The calculated energy barriers indicate that the para-position of phenol has higher reactivity than the ortho-position. The reaction occurs in a concerted mechanism. However, the process exhibits asynchronous characteristics, particularly the CC bond formation precedes the proton transfer and the proton transfer from water molecules to the carbonyl oxygen is ahead of proton abstraction from the benzene ring.

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Methanediol decomposition mechanisms: A study considering various ab initio approaches

Abstract: ABSTRACTrn

Cited by 17 publications

References 13 publications

Ab Initio Molecular Dynamics Study of the Reaction of Water with Formaldehyde in Sulfuric Acid Solution

Ab Initio Molecular Dynamics Study of the Reaction of Water with Formaldehyde in Sulfuric Acid Solution

Synthesis of methanediol [CH ₂ (OH) ₂ ]: The simplest geminal diol

A computational study on the reaction mechanism of neutral phenol with formaldehyde in aqueous solution

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Methanediol decomposition mechanisms: A study considering various ab initio approaches

Abstract: ABSTRACTrn

Cited by 17 publications

References 13 publications

Ab Initio Molecular Dynamics Study of the Reaction of Water with Formaldehyde in Sulfuric Acid Solution

Ab Initio Molecular Dynamics Study of the Reaction of Water with Formaldehyde in Sulfuric Acid Solution

Synthesis of methanediol [CH 2 (OH) 2 ]: The simplest geminal diol

A computational study on the reaction mechanism of neutral phenol with formaldehyde in aqueous solution

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Synthesis of methanediol [CH ₂ (OH) ₂ ]: The simplest geminal diol