Structure and vibrational spectra of vinyl ether conformers. The comparison of B3LYP and MP2 predictions

Ignatyev, Igor S.; Montejo, Manuel; Sundius, Tom; Ureña, Francisco Partal; González, Juan Jesús López

doi:10.1016/j.chemphys.2007.01.013

Cited by 11 publications

(9 citation statements)

References 34 publications

(49 reference statements)

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“…For instance, the MP2 calculations always provide the skew AC -form as a second isomer. The DFT B3LYP calculations with use of 6-31G(d) and 6-311G(d,p) basis sets give the same results, while addition of diffuse functions or using the correlation consistent ( aug )-cc-pVnZ basis sets turns the AP to be a major configuration …”

Section: Resultsmentioning

confidence: 75%

“…Early investigations , stated that the structure of aforementioned isomer corresponds to a skew anticlinal ( AC ) conformation, while AP -conformation corresponds to a low energy barrier between two shallow minima. Similar difficulties are associated with the study of rotational isomers of methyl vinyl ether, and in this case the problem is also far from the final solution (see ref and references therein). For instance, the MP2 calculations always provide the skew AC -form as a second isomer.…”

Section: Resultsmentioning

confidence: 91%

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Nucleophilic Addition of Ketones To Acetylenes and Allenes: A Quantum-Chemical Insight

et al. 2017

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A CBS-Q//B3 based study has been carried out to elucidate the mechanism of the KOH/DMSO superbase catalyzed ketones nucleophilic addition to alkyl propargyl and alkyl allenyl ethers yielding, along with (Z)-monoadducts, up to 26% of unexpected (E)-diadducts. The impact of different substrates (alkynes versus allenes) on the reaction mechanism has been discussed in detail. Along with the model reaction of acetone addition to propyne and allene, the addition of acetone and acetophenone to methyl propargyl and methyl allenyl ethers is considered. The limiting reaction stage of the starting ketone carbanion addition to propargyl and allenyl systems occurs with activation energies typical for vinylation of ketones. In contrast, the addition of intermediate α-carbanions to the terminal position of methyl allenyl ether is associated with unusually low activation barriers. The results obtained explain the composition of the reaction products and indicate the participation of mainly the allene form in the reaction.

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Section: Resultsmentioning

confidence: 75%

Section: Resultsmentioning

confidence: 91%

Nucleophilic Addition of Ketones To Acetylenes and Allenes: A Quantum-Chemical Insight

et al. 2017

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“…When the representation uses a localized Kekulé structure where the C1‐C2 bond is a double bond and C2‐C3 is a single bond, as shown in Figure , the presence of the methyl vinyl ether motif is clearer. As the preference for the syn conformation of methyl vinyl ether over the anti has been known for several decades, the observed preference for the bent conformation of 2‐OMe‐naphthalene should therefore not be a surprise.…”

Section: Figurementioning

confidence: 98%

Existence of a Preferred Orientation for the Methoxy Group on an Extended Aromatic System.

et al. 2018

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The conformations of a methoxy group introduced on naphthalene in position 2 has been investigated both experimentally (searches in crystallographic data, NOE measurements by NMR) and theoretically with ab initio calculations. While expected at first glance as being equivalent and predicted as such by force field methods, the two conformations where the methoxy is in the plane of the aromatic ring and turned either towards one or the other proton of naphthalene are actually very different in energy : ΔE=1.2 to 1.8 kcal mol−1, a surprisingly high value! The delocalization of the oxygen lone pair on the π‐system of the aromatic ring differs between the two conformers and is proposed to account predominantly for such unexpectedly large ΔE. It is our opinion that given the magnitude of the energies involved, force field methods should be corrected to take into account this conformational effect.

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“…An m23, and m16, were sufficiently populated at the room temperature of the experiment to readily observe rotational satellite lines. A section of the rotational spectrum showing the satellite pattern of the 16116 150 15 and 16016 151 15 pair is presented in Fig. 3.…”

Section: Ground State Rotational Spectrummentioning

confidence: 99%

“…The small A-E splittings arising from the coupling between methyl internal rotation and the overall rotation were resolved in the vibrational ground state using waveguide FTMW spectroscopy and a barrier to internal rotation of methyl group of 1256 cm -1 was derived [13]. Cis-methyl vinyl ether has three low-lying vibrational modes [14,15] involving skeletal CCAOC torsion (m24), OACH3 torsion (m23) and in-plane CAOAC bending mode (m16), depicted in Fig. 1a.…”

Section: Introductionmentioning

confidence: 99%

The millimeter and submillimeter wave spectrum of cis-methyl vinyl ether

Daly

Kolesníková

Mata

et al. 2014

Journal of Molecular Spectroscopy

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a b s t r a c t Among the species of potential interstellar relevance, methyl vinyl ether (CH3OCH@CH2) is the simplest ether compound containing both alkyl and alkene functional groups. In order to facilitate its detection in the ISM, we have measured the millimeter and submillimeter wave spectra from 50 to 650 GHz. We present the analysis of pure rotational spectrum of the cis-methyl vinyl ether in the vibrational ground state and in the first excited states of in-plane bending mode (m16) and methyl (m23) and skeletal (m24) torsional modes. Coriolis and Fermi type interactions between the v24 = 1 and v23 = 1 states have been explicitly treated using an effective two-state Hamiltonian.

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Structure and vibrational spectra of vinyl ether conformers. The comparison of B3LYP and MP2 predictions

Cited by 11 publications

References 34 publications

Nucleophilic Addition of Ketones To Acetylenes and Allenes: A Quantum-Chemical Insight

Nucleophilic Addition of Ketones To Acetylenes and Allenes: A Quantum-Chemical Insight

Existence of a Preferred Orientation for the Methoxy Group on an Extended Aromatic System.

The millimeter and submillimeter wave spectrum of cis-methyl vinyl ether

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