Structural and heat of formation studies of halogenated methyl hydro-peroxides

Kosmas, Agnie M.; Mpellos, Christos; Salta, Zoi; Drougas, Evangelos

doi:10.1016/j.chemphys.2010.03.026

Cited by 8 publications

(11 citation statements)

References 40 publications

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“…Like CH 3 OOH, the higherenergy anti conformer of CH 2 FOOH has a lower torsional barrier (0.8 kca/mol) and also no opportunity for hydrogen-bonding. The stabilization that lowers the potential minima is consistent with previous work thatshows fluoromethyl hydroperoxides to be thermodynamically stable, compared to other halogenated hydroperoxides[34].…”

supporting

confidence: 90%

“…Optimized conformers and barriers for torsion about the O-O bond.Optimized geometries have been determined in previous computational works[17,33,34], and findings here are similar. Following our work that distinguished contributions from different conformers in experimental overtone spectra[20], we consider anti and gauche conformers with respect to the X-C-O-O dihedral (X = F or H).…”

supporting

confidence: 76%

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Intramolecular hydrogen-bonding effects on O H stretch overtone excitation for fluorinated hydroperoxides

2017

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Applying computational methods for predicting gas-phase O-H stretch overtone spectra to the series of fluorinated hydroperoxides CF 3 OOH, CHF 2 OOH, and CH 2 FOOH reveals how intramolecular hydrogen bonding changes their overtone photochemistry, relative to their un-fluorinated analog CH 3 OOH. Intramolecular hydrogen bonding between fluorine and the hydroxyl hydrogen atom decreases O-H stretch frequencies and raises the barrier for torsion about the O-O bond. Whereas O-O torsion accompanies O-H stretch overtone excitation for CH 3 OOH, this is not the case for the fluorinated analogs that have intramolecular hydrogen bonding. The comparison highlights the molecular features that contribute to the feasibility of atmospheric overtone-induced O-O bond dissociation for CH 3 OOH, but not for its fluorinated analogs.

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supporting

confidence: 90%

supporting

confidence: 76%

Intramolecular hydrogen-bonding effects on O H stretch overtone excitation for fluorinated hydroperoxides

2017

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“…1). While there are no reports on radical reactions triggered by BBr 3 /O 2 , we speculate that the reaction mechanism might be analogous to the classical BR 3 /O 2 system in which the putative peroxy-boron species A is generated 49 at the initiation stage of the radical process (Fig. 1A) and corresponds to the new NMR signals (25.0 ppm in 11 B NMR and À2.68 ppm in 1 H NMR).…”

mentioning

confidence: 76%

Boron tribromide as a reagent for anti-Markovnikov addition of HBr to cyclopropanes

Gieuw

Chen

et al. 2020

Chem. Sci.

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“…1.447 (15) 93 (7) 1.366 (33) 97(6) MW [57,58] 1.445 (49) 99.5 (20) 1.380 (26) 96.3(78) HF/3-21G 1.470 [59] 130.0 [59] 1.457 [59] 110.5 [59] 1.447 [59] 94.5 [59] MP2/6-31G(d) 1.458 [60] 103.0 [60] 1.461 [a] 104.7…”

Section: Cf 3 O-oc(o)f Fc(o)o-oc(o)f Cf 3 C(o)o-oc(o)cf 3 and Cf 3 mentioning

confidence: 97%

“…Only in CF 3 OOC(O)F a small contribution of 3 % anti conformer was detected by IR-matrix spectroscopy. [68] The experimental OÀO [59] 130.0 [59] 1.457 [59] 110.5 [59] 1.447 [59] 94.5 [59] MP2/6-31G(d) 1.458 [60] 103.0 [60] [46] 98.6 [46] For the three peroxides with two C(O)X groups IR-matrix spectroscopy and GED observed only a single syn-syn conformation with both C=O bonds in syn orientation. In CF 3 OC(O)O-OC(O)OCF 3 the OÀCF 3 bonds are also oriented syn with respect to the C=O bonds, leading to a syn-syn-syn-syn structure (see These peroxynitrates possess very similar OÀO bond lengths, between 1.408(8) and 1.420 (6) and NÀO bond lengths be-tween 1.497 (7) in CH 3 C(O)O-ONO 2 and 1.526 (10) in CF 3 C(O)O-ONO 2 .…”

Section: Hc(o)o-ohmentioning

confidence: 97%

Gas Phase Structures of Peroxides: Experiments and Computational Problems

Oberhammer

2014

ChemPhysChem

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Gas-phase structures of several organic and inorganic peroxides X-O-O-X and X-O-O-X', which have been determined experimentally by gas electron diffraction and/or microwave spectroscopy, are discussed. The OO bond length in these peroxides varies from 1.481(8) Å in Me3 SiOOSiMe3 to 1.214(2) Å in FOOF and the dihedral angle ϕ(XO-OX) between 0° in HC(O)O-OH and near 180° in Bu(t) O-OBu(t) . Some of the peroxides cause problems for quantum chemistry, since several computational methods fail to reproduce the experimental structures. Extreme examples are MeO-OMe and FO-OF. In the case of MeO-OMe only about half of the more than 100 computational methods reported in the literature reproduce the experimentally determined double-minimum shape of the torsional potential around the OO bond correctly. For FO-OF only a small number of close to 200 computational methods reproduce the OO and OF bond lengths better than ±0.02 Å.

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Structural and heat of formation studies of halogenated methyl hydro-peroxides

Cited by 8 publications

References 40 publications

Intramolecular hydrogen-bonding effects on O H stretch overtone excitation for fluorinated hydroperoxides

Intramolecular hydrogen-bonding effects on O H stretch overtone excitation for fluorinated hydroperoxides

Boron tribromide as a reagent for anti-Markovnikov addition of HBr to cyclopropanes

Gas Phase Structures of Peroxides: Experiments and Computational Problems

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