Proton Affinity and Heat of Formation of Vinyloxy [CH2CHO]. and Acetonyl [CH2COCH3]. Radicals

Bouchoux, Guy; Chamot‐Rooke, Julia; Leblanc, Danielle; Mourgues, P.; Sablier, Michel

doi:10.1002/1439-7641(20010417)2:4<235::aid-cphc235>3.3.co;2-j

Cited by 22 publications

(45 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Furthermore, their further ligand exchange reactions with the keto-compounds M in the cell, leads to [M, NH 4 ϩ ] products. These observations are in agreement with the known relative proton affinities of the CH 2 ϭCHO ⅐ and CH 2 ϭC(CH 3 )O ⅐ radicals [15] on the one hand and of ammonia [16] on the other, and they strongly suggest that the ammonia solvated CH 2 ¢CHOH ϩ⅐ and CH 2 ¢C(CH 3 …”

Section: Structure Of the Mclafferty Productsupporting

confidence: 88%

Reactions of [NH₃^+·, H₂O] with carbonyl compounds: A McLafferty rearrangement within a complex?

Rest

Jensen

Azeim

et al. 2004

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

The reactions of the water solvated ammonia radical cation [NH 3 ⅐ϩ , H 2 O] with a variety of aldehydes and ketones were investigated. The reactions observed differ from those of low energy aldehydes and ketones radical cations, although electron transfer from the keto compound to ionized ammonia is thermodynamically allowed within the terbody complexes initially formed. The main process yields an ammonia solvated enol with loss of water and an alkene. This process corresponds formally to a McLafferty fragmentation within a complex. With aldehydes, another reaction can take place, namely the transfer of the hydrogen from the CHO group to ammonia, leading to the proton bound dimer of ammonia and water, and to the NH 4 ϩ cation. Comparison between the available experimental results leads to the conclusion that the McLafferty fragmentation occurs within the terbody complex initially formed, with no prior ligand exchange, the water molecule acting as a spectator partner. (J Am Soc Mass Spectrom 2004, 15, 966 -971) T he study of the unimolecular and bimolecular reactivity of solvated radical cations requires access to such kind of species. Of course, by direct reactions between an ion and a solvent molecule in the cell of an ion cyclotron resonance mass spectrometer (FT-ICR), an encounter complex is formed in which reactions can take place. However, the solvated radical cations formed in this way possess a high energetic content (at least equal to the solvation energy) and are too short lived to be isolated and studied. Furthermore, since these species are hot ions, their fragmentations correspond to the unimolecular reactions which are entropically favored. Therefore, the reactions observed are not necessarily the same as those of long lived solvated radical cations, as demonstrated in the case of the CH 2 CHOH ⅐ϩ /CH 3 CHO system [1], where the acetaldehyde solvated enol ion is produced by reaction of the enol ion with paraldehyde (eq 1). In this case, the hot intermediate reacts by H ϩ transfer, whereas low energy collision induced dissociation of the solvated complex leads to H ⅐ abstraction [1]. CH 2 CHOH ⅐ϩ ϩ (CH 3 CHO) 3 3 [CH 2 CHOH ⅐ϩ , CH 3 CHO] ϩ (CH 3 CHO) 2 (1)

show abstract

Section: Structure Of the Mclafferty Productsupporting

confidence: 88%

Reactions of [NH₃^+·, H₂O] with carbonyl compounds: A McLafferty rearrangement within a complex?

Rest

Jensen

Azeim

et al. 2004

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

show abstract

“…The fundamental interest stems substantially from the recognition that the radical site in acetonyl is partially delocalized over the carbonyl double bond. [8][9][10][11] This property of the acetonyl radical may give rise to unusual kinetic features allowing the investigation of structure-activity relationships. Despite this importance and interest, only few studies have been performed so far on the kinetics of the reactions of the acetonyl radical.…”

Section: Introductionmentioning

confidence: 99%

Laser spectrometry and kinetics of selected elementary reactions of the acetonyl radical

Imrik

Farkas

Vasvári

et al. 2004

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

“…However, this energy is less at enols. For vinyl alcohol BDE(O-H) is 3.65 eV [16]. The bond length O-H at (hfac) is 0,988•10 -10 m [17].…”

Section: Resultsmentioning

confidence: 98%

Chemical Bonds Dissociation Energy

Iakubov¹

2017

Preprint

View full text Add to dashboard Cite

In previous publications dealing with experimental mass spectrometry of tungsten hexacarbonyl, hexafluoroacetylacetone and its bidentate metal complexes M(hfac) 2 ; M = Cu, Pd the obtained data have been not adequately systematized. In this paper, we analyse the previously published experimental data of the various bond dissociation energy. A modified Yukawa potential, which is the exact solution of the problem dependence the chemical bond energy of its length, is used to analyse the experimental data. Experimental results of the formation of ions can be interpreted only in terms of the formation of fractionally charged quasiparticles. As an experimental technique, mass spectrometry of negative ions in electron resonance capture mode ranks next to the fractional quantum Hall effect in which fractional values of the charge quantization are observed. Also noted the resonance possibility capture of electron with "negative" kinetic energy.The recent reports of Wnorowski et al. [1,2] on investigations of the decay of tungsten hexacarbonyl, W(CO) 6 , using electron ionization (EI)[1] and dissociative electron attachment (DEA)[2] methods were of particular interest to the low-temperature plasma and nanotechnology communities. Furthermore, the dissociative photoionisation of W(CO) 6 was, however, discussed in an earlier paper.[3] It was shown that the bond dissociation of [W(CO) n + ]-CO (n = 0-5) most likely proceeds differently if n < 3 or if n ≥ 3 and that the dissociation occurs from both vibrational excited states or from the electronic-vibrational excited states. The interaction of lowenergy electrons with W(CO) 6 was, however, discussed in a much earlier paper.[4] Our interest here is with the predominantly sequential detachment of a CO ligand from W(CO) 6 , as well as presenting a comparison of the chemical bond dissociation energy BDE(W−CO) as calculated with the EI and DEA processes.In Ref.

show abstract

Proton Affinity and Heat of Formation of Vinyloxy [CH2CHO]. and Acetonyl [CH2COCH3]. Radicals

Cited by 22 publications

References 0 publications

Reactions of [NH₃^+·, H₂O] with carbonyl compounds: A McLafferty rearrangement within a complex?

Reactions of [NH₃^+·, H₂O] with carbonyl compounds: A McLafferty rearrangement within a complex?

Laser spectrometry and kinetics of selected elementary reactions of the acetonyl radical

Chemical Bonds Dissociation Energy

Contact Info

Product

Resources

About

Proton Affinity and Heat of Formation of Vinyloxy [CH2CHO]. and Acetonyl [CH2COCH3]. Radicals

Cited by 22 publications

References 0 publications

Reactions of [NH3+·, H2O] with carbonyl compounds: A McLafferty rearrangement within a complex?

Reactions of [NH3+·, H2O] with carbonyl compounds: A McLafferty rearrangement within a complex?

Laser spectrometry and kinetics of selected elementary reactions of the acetonyl radical

Chemical Bonds Dissociation Energy

Contact Info

Product

Resources

About

Reactions of [NH₃^+·, H₂O] with carbonyl compounds: A McLafferty rearrangement within a complex?

Reactions of [NH₃^+·, H₂O] with carbonyl compounds: A McLafferty rearrangement within a complex?