“Stripping” the Carbon Atom of Methyl Halide by a Cationic Holmium Complex: A Gas-Phase Study

2015 ◽  
Vol 21 (41) ◽  
pp. 14305-14308 ◽  
Author(s):  
Shaodong Zhou ◽  
Maria Schlangen ◽  
Jilai Li ◽  
Xiao-Nan Wu ◽  
Helmut Schwarz
Keyword(s):  
Carbon Atom ◽  
Gas Phase ◽  
Phase Study ◽  
Methyl Halide

A gas phase study of the regioselective BH4− reduction of some 2-substituted maleic anhydrides

1988 ◽  
Vol 66 (10) ◽  
pp. 2587-2594 ◽  
Author(s):  
Hans van der Wel ◽  
Nico M. M. Nibbering ◽  
Margaret M. Kayser
Keyword(s):  
Carbon Atom ◽  
Gas Phase ◽  
Ion Cyclotron Resonance ◽  
Ion Transfer ◽  
Hydride Ion ◽  
Ion Molecule Reactions ◽  
Phase Study ◽  
Olefinic Double Bond ◽  
Gas Phase Ion ◽  
Hydride Ion Transfer

Gas phase ion/molecule reactions in a Fourier transform ion cyclotron resonance mass spectrometer have been carried out for reductions of isotopically labelled citraconic (methylmaleic), phenylmaleic, and ethoxymaleic anhydrides by BH4−. In citraconic anhydride the carbonyl group neighbouring the methyl substituent is reduced preferentially in agreement with the ab initio calculations, which show the higher LUMO coefficients at this site. Hydride ion transfer to the olefinic double bond occurs as well; however, in that case no preference for either of the carbon atoms is observed. In phenylmaleic anhydride strong indications are found for a theoretically unexpected hydride ion transfer to the phenyl ring. For ethoxymaleic anhydride experimental evidence is presented showing hydride ion transfer to the carbon atom carrying the ethoxy group, which is in agreement with the "best overlap" consideration predicting that this carbon atom bears the highest LUMO coefficient.Most of the hydride transfers from BH4− to the molecules studied seem, therefore, to take place under orbital control rather than under control of long-range ion-induced dipole interactions between reactants.

Gas phase study of a 2-chloro-p-xylene discharge

2010 ◽  
Author(s):  
Isabel C Estrada-Raygoza ◽  
Gabriel Padron-Wells ◽  
Lawrence J. Overzet ◽  
Matthew J. Goeckner
Keyword(s):  
Gas Phase ◽  
Phase Study

scholarly journals Infrared gas phase study on plasma-polymer interactions in high-current diffuse dielectric barrier discharge

2017 ◽  
Vol 121 (24) ◽  
pp. 243301 ◽  
Author(s):  
Y. Liu ◽  
S. Welzel ◽  
S. A. Starostin ◽  
M. C. M. van de Sanden ◽  
R. Engeln ◽  
...  
Keyword(s):  
Gas Phase ◽  
Dielectric Barrier Discharge ◽  
Barrier Discharge ◽  
Plasma Polymer ◽  
High Current ◽  
Dielectric Barrier ◽  
Phase Study ◽  
Polymer Interactions

Thermochemistry of Elementary Actinide Sulfide Molecules: A Gas-Phase Study of Curium Sulfide

2010 ◽  
Vol 1264 ◽  
Author(s):  
Cláudia C. L. Pereira ◽  
Joaquim Marçalo ◽  
John K. Gibson
Keyword(s):  
Gas Phase ◽  
Bond Dissociation Energies ◽  
Gas Phase Reactions ◽  
General Applicability ◽  
Molecular Systems ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Phase Study ◽  
Fundamental Understanding ◽  
Actinide Ions

AbstractExperiments to explore the reactivity and thermochemistry of elementary transuranium sulfide molecules have been initiated to expand the basis for a fundamental understanding of actinide bonding, and to enable the development of advanced theoretical methodologies which will be of general applicability to more complex molecular systems. Bimolecular gas-phase reactions between transuranium actinide ions and neutral reagents are employed to obtain thermochemical information. The initial actinide sulfide studies have focused on obtaining the 298 K bond dissociation energy for the CmS+ ion, D[Cm+-S] = 475±37 kJ mol-1; from this result and an estimate of IE[CmS] ≈ IE[CmO] + 0.5 eV, we obtain D[Cm-S] = 563±64 kJ mol-1. The bond dissociation energies, D[Cm+-S] and D[Cm-S] are approximately 200 kJ mol-1 and 150 kJ mol-1 lower than for the corresponding oxides, CmO+ and CmO. The nature of the bonding in the CmS+ ion appears to be generally similar to that in other oxophilic metal sulfides. Comparisons with previous bond dissociation energies reported for ThS and US may suggest a difference in the An-S bonds for these early actinide sulfides as compared with CmS.

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