ChemInform Abstract: Formyl Cyanide. Synthesis by Retro‐Ene Cleavage of Allyloxyacetonitrile and Spectroscopic Properties

Vallée, Yannick; Ripoll, Jean‐Louis; Lacombe, Sylvie; Pfister‐Guillouzo, G.

doi:10.1002/chin.199028109

Cited by 5 publications

(15 citation statements)

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“…The short path thermolysis system has been described elsewhere. 33 Products are introduced at a partial pressure around 10 -2 mbar. In these conditions, it is estimated that the detection of decomposition products with lifetimes in the 10 -1 -10 -3 s range may be performed.…”

Section: Experimental Section and Calculation Methodsmentioning

confidence: 99%

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Sulfenic Acids in the Gas Phase: A Photoelectron Study

et al. 1996

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Thermolysis of methyl methanethiosulfinate and methyl tert-butyl sulfoxide has been studied by photoelectron (PE) spectroscopy. The electronic structure of methanesulfenic acid (1) generated from both compounds has been determined, and the thermal stability of 1 was checked. 1 appears rather stable in the gas phase, giving rise to thioformaldehyde and water at high temperature. Thermolysis of vinyl tert-butyl sulfoxide gives rise to ethanethial S-oxide (6). At the thermolysis onset, sulfine 6 is observed in a mixture with a compound identified as ethenesulfenic acid (4). These results imply either an easy isomerization of 4 to 6, in agreement with previous theoretical evaluations, or an alternative thermolysis pathway of the starting sulfoxide, directly leading to sulfine 6. The obtained PE spectra complement previous microwave and/or mass spectrometry data and provide a further insight in the electronic structure and thermal stability of sulfenic acids 1 and 4. The experimental ionization potentials are compared throughout this study with ab-initio calculated vertical ionization potentials either within Koopmans' approximation or by difference between the ionic and ground state energies.

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Section: Experimental Section and Calculation Methodsmentioning

confidence: 99%

“…The IPs are accurate within 0.02 eV. The short path thermolysis system has been described elsewhere . Products are introduced at a partial pressure around 10 -2 mbar.…”

Section: Experimental Section and Calculation Methodsmentioning

confidence: 99%

Sulfenic Acids in the Gas Phase: A Photoelectron Study

et al. 1996

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“…The photoelectron spectra were recorded on a Helectros 0078 spectrometer fitted with a shortpath coupled FVT oven, as already described (2). We used the HF method at the MP2 level (4) with conjunction with the 6-311G(d, p) basis set, and the functional density theory (5) with the BP86 functional (GAUSSIAN 94 (6)).…”

Section: Methodsmentioning

confidence: 99%

Gas-Phase Generation and Photoelectron Spectra of Reactive Unsubstituted Cycloalkenethiones

Chrostowska

Miqueu

Pfister‐Guillouzo

et al. 2001

Journal of Molecular Spectroscopy

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“…Moreover, the two lowest lying vibrational bands of the ground electronic state and a number of excited electronic state vibrational bands were identified. This study stimulated further interest in the spectroscopic properties of formyl cyanide, since rotationally resolved electronic and infrared spectra could be obtained for this molecule. − The analogous thioformyl cyanide has been formed as a transient species by a number of routes, including treatment of the appropriate Bunte salt, NCCH 2 SSO 3 Na, with triethylamine and calcium chloride and photolysis of C 6 H 5 COCH 2 SCH 2 CN , More recently, thioformyl cyanide was formed by thermal decomposition of CH 2 CHCH 2 SCH 2 CN and characterized in detail with the use of photoelectron spectroscopy …”

Section: Introductionmentioning

confidence: 99%

“…This study stimulated further interest in the spectroscopic properties of formyl cyanide, since rotationally resolved electronic and infrared spectra could be obtained for this molecule. [2][3][4][5][6][7][8] The analogous thioformyl cyanide has been formed as a transient species by a number of routes, including treatment of the appropriate Bunte salt, NCCH 2 SSO 3 Na, with triethylamine and calcium chloride 9 and photolysis of C 6 H 5 COCH 2 SCH 2 CN. 10 The existence of thioformyl cyanide in these studies was inferred from the formation of cycloadducts with an appropriate 1,3diene.…”

Section: Introductionmentioning

confidence: 99%

Experimental Determination of the Enthalpies of Formation of Formyl Cyanide and Thioformyl Cyanide in the Gas Phase

1996

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The enthalpies of formation of formyl cyanide (HC(O)CN) and thioformyl cyanide (HC(S)CN) in the gas phase have been determined with the use of Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. The enthalpy of formation, ∆H f°( 298 K), of formyl cyanide is determined to be 26 ( 20 kJ mol -1 , whereas the value for thioformyl cyanide is 222 ( 30 kJ mol -1 . These enthalpies of formation are derived from experimental values of (i) the gas-phase acidities of the methylene groups in the CH 3 OCH 2 CN and CH 3 SCH 2 CN species (∆H°a cid (CH 3 OCH 2 CN) ) 1556 ( 8 kJ mol -1 and ∆H°a cid (CH 3 SCH 2 CN) ) 1494 ( 8 kJ mol -1 ), (ii) the enthalpy change for the dissociation of the CH 3 OC h HCN and CH 3 SC h HCN carbanions into a methyl radical and the radical anion of formyl cyanide and thioformyl cyanide, respectively (BDE-(CH 3 OC h HCN) ) 116 ( 10 kJ mol -1 and BDE(CH 3 SC h HCN) ) 133 ( 10 kJ mol -1 ), and (iii) the electron affinities of the neutral formyl species (EA(HC(O)CN) ) 65 ( 3 kJ mol -1 and EA(HC(S)CN) ) 159 ( 15 kJ mol -1 ). The structures of the two carbanions and the radical anions of the (thio)formyl species have been ascertained by high kinetic energy (8 keV) collision-induced charge-reversal (CR) experiments performed with the use of a double-focusing quadrupole hybrid mass spectrometer.

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ChemInform Abstract: Formyl Cyanide. Synthesis by Retro‐Ene Cleavage of Allyloxyacetonitrile and Spectroscopic Properties

Abstract: 109ChemInform Abstract (PE, IR, UV; in part no yields given).

Cited by 5 publications

References 0 publications

Sulfenic Acids in the Gas Phase: A Photoelectron Study

Sulfenic Acids in the Gas Phase: A Photoelectron Study

Gas-Phase Generation and Photoelectron Spectra of Reactive Unsubstituted Cycloalkenethiones

Experimental Determination of the Enthalpies of Formation of Formyl Cyanide and Thioformyl Cyanide in the Gas Phase

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