First Synthesis and Characterization by Mass Spectrometry and UV‐Photoelectron Spectroscopy of Methylenearsane

Chrostowska, Anna; Dargelos, Alain; Lemierre, Virginie; Sotiropoulos, Jean‐Marc; Guénot, Pierre; Guillemin, Jean‐Claude

doi:10.1002/anie.200352445

Cited by 10 publications

(13 citation statements)

References 28 publications

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“…In our approach, we compare the accuracy of the calculations and the "shapes" of the predicted and experimental spectra. Our method has also been shown to perform very well by other investigators (13). Consequently, we saw no need to do an extensive time-consuming study with all the other computational methods.…”

Section: Resultsmentioning

confidence: 80%

UV photoelectron spectroscopic and computational study of 7-substituted cycloheptatrienes

Bajorek¹

2008

Can. J. Chem.

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The He(I) photoelectron (PE) spectra of cycloheptatriene (1), 7-methylcycloheptatriene (2), 7-methoxycycloheptatriene (3), 7-methylthiocycloheptatriene (4), and 7-diemthylaminocycloheptatriene (5) were recorded and interpreted using MO energies and ionization potentials acquired from B3PW91 calculations. Partial simulated PE spectra were in good agreement with the experimental results. The axial and equatorial conformers have distinct PE spectra as illustrated by simulation. The PE spectra of 2, 3, and 5 are representative of the equatorial conformers, while the PE spectrum of 4 was in accord with a 1:1 mixture of equatorial and axial conformational isomers based on spectral simulation. The calculated free energy differences between the equatorial and axial conformers are in the order of 2 kcal mol -1 (1 cal = 4.184 J) for compounds 2, 3, and 5, where the equatorial conformational isomer is lowest in energy. In the case of 4, the equatorial conformer was only marginally lower in energy than its axial counterpart, where the free energy difference is 0.1 kcal mol -1 .Résumé : On a enregistré les spectres photoélectroniques (PE) He(I) du cycloheptatriène (1), du 7-méthyl-cycloheptatriène (2), du 7-méthoxycycloheptatriène (3) et du 7-méthylthiocycloheptatriène (4) et on les interprète en faisant appel aux énergies des orbitales moléculaires (OM) et des potentiels d'ionisation obtenus par des calculs B3PW91. Les spectres PE simulés partiels sont en bon accord avec les résultats expérimentaux. Tels qu'illustrés par la simulation, les conformères axiaux et équatoriaux présentent des spectres PE distincts. Les spectres PE des produits 2, 3 et 5 sont représentatifs de conformères équatoriaux alors que le spectre PE du composé 4 correspond au spectre de simulation d'un mélange 1:1 des isomères conformationnels équatoriaux et axiaux. Les différences d'énergie libre entre les conformères équatorial et axial sont de l'ordre de 2 kcal mol -1 pour les conformères équatoriaux des composés 2, 3 et 5. Dans le cas du produit 4, le conformère équatorial n'est que marginalement favorisé par une différence d'énergie de 0,1 kcal mol -1 par rapport au conformère axial.Mots-clés : cycloheptatriènes substitués en position 7, spectroscopie photoélectronique He(I), B3PW91, simulation spectrale.[Traduit par la Rédaction] Bajorek and Werstiuk 450

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Section: Resultsmentioning

confidence: 80%

UV photoelectron spectroscopic and computational study of 7-substituted cycloheptatrienes

Bajorek¹

2008

Can. J. Chem.

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“…16 This reaction is very sensitive to each parameter. The use of potassium carbonate instead of sodium carbonate or a higher temperature of dehydrohalogenation leads to the competitive reaction of reduction and the formation of methylarsine.…”

Section: Resultsmentioning

confidence: 99%

“…Only recently, some 20 years after the synthesis of the methylenephosphine, we reported the synthesis of the methylenearsine formed by dehydrohalogenation of gaseous chloromethylarsine on a solid base using VGSR conditions. 16 The characterization was performed in the gaseous phase by high-resolution MS (HRMS) and UV-PES. These spectroscopic data are compared with the photoelectron spectrum of methylenephosphine.…”

Section: Resultsmentioning

confidence: 99%

Ionization potentials of heteroalkenes: a comparative study

Chrostowska

Lemierre

Dargelos

et al. 2004

Applied Organom Chemis

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Methanimine, methylenephosphine and methylenearsine have been prepared in the gas phase and the gaseous flow has been analyzed by spectroscopy. Photoelectron spectra have been recorded and we report here a comparative study on these spectra. This comparison has been extended to the corresponding derivatives with a triple bond: hydrogen cyanide and methylidynephosphine. Estimation by theoretical calculations of the ionization potentials of the unknown methylidynearsine has been proposed.

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“…UV photoelectron spectroscopy (UV‐PES) or mass spectrometry (MS), coupled with adapted experimental methods, such as flash vacuum thermolysis (FVT) in high‐vacuum conditions, are ideally suited to the observation of highly reactive organometallic intermediates. Supported by calculations, UV‐PES can provide an accurate complete description of the electronic structures of new systems, especially those involving new bonding situations …”

Section: Introductionmentioning

confidence: 99%

Short‐Lived Orthobenzyne Complexes with Early Transition Metals of Group IV. First Direct Characterization and Electronic Cartography by Coupling FVT/UV‐PES with Calculations

et al. 2018

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Short-lived η 2 -benzyne metallocene complexes [Cp 2 M(η 2 -c-C 6 H 4 )] with group IV metals are important intermediates in organic chemistry, their olefin insertion products being building blocks for aromatic and heterocyclic compounds. For the first time, an electronic cartography of these short-lived species has been obtained through the determination of their ionization potentials. They have been directly characterized in the gas phase by UV photoelectron spectroscopy, by monitoring, in situ, the thermal -H abstraction of benzene from [a]

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First Synthesis and Characterization by Mass Spectrometry and UV‐Photoelectron Spectroscopy of Methylenearsane

Cited by 10 publications

References 28 publications

UV photoelectron spectroscopic and computational study of 7-substituted cycloheptatrienes

UV photoelectron spectroscopic and computational study of 7-substituted cycloheptatrienes

Ionization potentials of heteroalkenes: a comparative study

Short‐Lived Orthobenzyne Complexes with Early Transition Metals of Group IV. First Direct Characterization and Electronic Cartography by Coupling FVT/UV‐PES with Calculations

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