Aminohydroxymethylene (H<sub>2</sub>N–C̈–OH), the Simplest Aminooxycarbene

Bernhardt, Bastian; Ruth, Marcel; Reisenauer, Hans Peter

doi:10.1021/acs.jpca.1c06151

Cited by 8 publications

(25 citation statements)

References 55 publications

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“…Very recently, a trans -aminohydroxymethylene carbene was synthesized, H 2 N–C̈–OH, by pyrolysis of oxalic acid monoamide and trapping in solid argon. 80 IR spectra at 3 K together with a computed anharmonic spectrum at B3LYP/6-311++G(3df,3pd) enabled the identification. Geometrically, ∠OC̈N = 107.8°, d (O–C̈) = 1.347 Å, and d (C̈–N) = 1.322 Å; these compare well with the values for hydroxy(methylamino), viz.…”

Section: Resultsmentioning

confidence: 99%

C₂H₅NO Isomers: From Acetamide to 1,2-Oxazetidine and Beyond

Simmie

2022

J. Phys. Chem. A

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This work documents the properties of a number of isomers of molecular formula C 2 H 5 NO from the most stable, acetamide, through 1,2-oxazetidine and including even higher energy species largely of a dipolar nature. Only two of the isomers have been detected in emissions from the interstellar medium (ISM); possible further candidates are identified, and the likelihood of their being detectable is considered. In general, hardly any of these compounds have been discussed in the existing chemical literature, so this work represents an important contribution extending the canon of chemical bonding which can contribute to machine learning, providing a more exacting test of AI applications. The presence in the ISM of acetamide, CH 3 C(O)NH 2 , is the subject of current debate with no clear and obvious paths to its formation; it is shown that a 1,3-[H]-transfer from ( E,Z )-ethanimidic acid, CH 3 C(OH)=NH, is feasible in spite of an energy barrier of 130 kJ mol –1 . It is speculated that imidic acid can itself be formed from abundant precursors, H 2 O and CH 3 C≡N, in an acid-induced, water addition, autocatalytic reaction on water–ice grains. H 3 CC≡N H 3 CC≡NH + + H 2 O H 3 CC(O + H 2 )=NH H 3 CC(OH)=NH + H 3 O +

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Section: Resultsmentioning

confidence: 99%

C₂H₅NO Isomers: From Acetamide to 1,2-Oxazetidine and Beyond

Simmie

2022

J. Phys. Chem. A

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“…Energies given in the table are relative to the lower energy trans isomer of aminohydroxymethylene (AHM- t ) and are zero-point energy (ZPE) corrected. Results of the CCSD(T)/cc-pVTZ level of calculations reported earlier are also given in the table for comparison. Mean absolute deviations of the stationary point energies computed using density functional methods with respect to the CCSD(T) results were found to be 2.3, 2.7, 3.1, and 3.5 kcal/mol for B3LYP, Becke97-1, PBE0, and M06-2X functionals, respectively.…”

Section: Methodsmentioning

confidence: 99%

“…AHM has been invoked as a possible intermediate in the interstellar reaction of HCN (HNC) + H 2 O. Substituted analogues of this molecule are known in the literature, , but the unsubstituted AHM was only recently synthesized as a stable molecule . The corresponding radical cation (H 2 N–C–OH) .+ has been prepared in mass spectrometry experiments , and its unimolecular reactivity studied by electronic structure calculations …”

Section: Introductionmentioning

confidence: 99%

Theoretical Investigation of Dissociation versus Intramolecular Rearrangements in Aminohydroxymethylene

Paranjothy

2022

J. Phys. Chem. A

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Aminohydroxymethylene (H2N–C̈–OH) is the simplest aminooxycarbene which is a heteroatom stabilized carbene. This highly reactive molecule was prepared in an Ar matrix in a recent experimental work. Unimolecular reactivity of this astrochemically important molecule was investigated and only fragmentations were identified contrary to the observations of both fragmentations and intramolecular rearrangements in other hydroxycarbenes. These rearrangement reactions form the corresponding imine and carbonyl compounds. In the present work, direct chemical dynamics simulations of unimolecular chemistry of aminohydroxymethylene were performed in the gas phase to study atomic level dissociation mechanisms. Classical trajectories were generated on-the-fly using potentials and gradients computed at the density functional B3LYP/6-31+G* level of electronic structure theory. Simulation results showed that intramolecular rearrangements accompany fragmentations during the unimolecular decay process of aminohydroxymethylene. However, the average lifetime of the intermediate isomers were found to be only few picoseconds which might not have been long enough for detection in the experiments.

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“…Very recently a trans aminohydroxymethylene carbene has been synthesised, H 2 N -C -OH, by pyrolysis of oxalic acid monoamide and trapping in solid argon. 70 IR spectra at 3 K together with a computed anharmonic spectrum at B3LYP/6-311++G(3df,3pd) enabled the identification. Geometrically, ∠O CN = 107.8…”

Section: Carbenes Hydroxy(methylamino) Carbenementioning

confidence: 99%

C2H5NO Isomers: from Acetamide to1,2-Oxazetidine and Beyond

Simmie

2021

Preprint

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This work documents the properties of a number of isomers of molecular formula C2H5NO from the most stable, acetamide, through 1,2-oxazetidine and including even higher energy species largely of a dipolar nature. Only two of the isomers have been detected in emissions from the interstellar medium (ISM); possible further candidates are identifi�ed and the likelihood of their being detectable are considered. In general hardly any of these compounds have featured in the existing chemical literature so this work represents an important contribution extending the canon of chemical bonding which can contribute to machine-learning | providing a more exacting test of AI applications. The presence of acetamide, CH3C(O)NH2, is the subject of current debate with no clear and obvious paths to its formation; it is shown that a 1,3[H]-transfer from (E,Z ) ethanimidic acid, CH3C(OH){{NH, is feasible in spite of an energy barrier of 130 kJ/mol. It is speculated that the imidic acid can itself be formed from abundant precursors, H2O and CH3C{{{N, in an acid-induced, water addition, auto-catalytic reaction on water-ice grains.

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Aminohydroxymethylene (H₂N–C̈–OH), the Simplest Aminooxycarbene

Cited by 8 publications

References 55 publications

C₂H₅NO Isomers: From Acetamide to 1,2-Oxazetidine and Beyond

C₂H₅NO Isomers: From Acetamide to 1,2-Oxazetidine and Beyond

Theoretical Investigation of Dissociation versus Intramolecular Rearrangements in Aminohydroxymethylene

C2H5NO Isomers: from Acetamide to1,2-Oxazetidine and Beyond

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Aminohydroxymethylene (H2N–C̈–OH), the Simplest Aminooxycarbene

Cited by 8 publications

References 55 publications

C2H5NO Isomers: From Acetamide to 1,2-Oxazetidine and Beyond

C2H5NO Isomers: From Acetamide to 1,2-Oxazetidine and Beyond

Theoretical Investigation of Dissociation versus Intramolecular Rearrangements in Aminohydroxymethylene

C2H5NO Isomers: from Acetamide to1,2-Oxazetidine and Beyond

Contact Info

Product

Resources

About

Aminohydroxymethylene (H₂N–C̈–OH), the Simplest Aminooxycarbene

C₂H₅NO Isomers: From Acetamide to 1,2-Oxazetidine and Beyond

C₂H₅NO Isomers: From Acetamide to 1,2-Oxazetidine and Beyond