Bimolecular reactions of nucleophiles in the gas phase. The reaction of the methoxide anion with ketones. An ion cyclotron resonance study

1980 ◽  
Vol 33 (10) ◽  
pp. 2271 ◽  
Author(s):  
G Klass ◽  
JH Bowie
Keyword(s):  
Gas Phase ◽  
Cyclotron Resonance ◽  
Ion Cyclotron Resonance ◽  
Bimolecular Reactions ◽  
Methyl Nitrite ◽  
Ion Molecule Reactions ◽  
Ion Cyclotron ◽  
Methoxide Anion

The methoxide anion (produced from methyl nitrite) reacts with neutral ketones (M) to form non-decomposing(M-H+)- ions. The (M-H+)- ions are ambident species and they undergo a number of ion-molecule reactions, including (i) characteristic reactions through the carbanion centre with methyl nitrite, and (ii) for acetone, the formation of an [M +(M- H+)]- ion. In several cases peaks due to collision-stabilized (M+MeO-) ions are observed (e.g. MeO-/acetone), but they are not detected for the majority of cases studied.

Thermodynamic control in the reactions of gas phase anions. An abinitio and ion cyclotron resonance study of the reactions of anions with diborane

1985 ◽  
Vol 63 (2) ◽  
pp. 281-287 ◽  
Author(s):  
O. Elsenstein ◽  
M. Kayser ◽  
M. Roy ◽  
T. B. McMahon
Keyword(s):  
Gas Phase ◽  
Cyclotron Resonance ◽  
Reaction Pathway ◽  
Basis Set ◽  
Resonance Spectroscopy ◽  
Ion Cyclotron Resonance ◽  
Ion Molecule Reactions ◽  
Ion Cyclotron ◽  
Reaction Channels ◽  
Gas Phase Ion

The gas phase ion molecule reactions of a number of anions, X−, with diborane, B2H6 have been investigated using ion cyclotron resonance spectroscopy. Two distinct reaction channels are observed in addition to simple proton transfer. The first of these is production of BH4− and BH2X while the second is formation of BH3X− and BH3. In order to determine the importance of thermodynamic factors in the course of reaction abinitio calculations have been carried out on the species involved to obtain the relative stabilities of the two possible pairs of products. The 4-31 +G basis set incorporating additional flat s and p functions has been used since this basis set has been demonstrated to give the most accurate description of anions to date. The results obtained indicate that the thermochemical factors are instrumental in determining the reaction pathway.

Bimolecular production of gas phase ionic hydrates by ion cyclotron resonance spectroscopy

1980 ◽  
Vol 58 (8) ◽  
pp. 863-865 ◽  
Author(s):  
R. L. Clair ◽  
T. B. McMahon
Keyword(s):  
Gas Phase ◽  
Cyclotron Resonance ◽  
Resonance Spectroscopy ◽  
Ion Cyclotron Resonance ◽  
Ion Chemistry ◽  
Ion Molecule Reactions ◽  
Hydronium Ion ◽  
Dominant Feature ◽  
Ion Cyclotron ◽  
Gas Phase Ion

The gas phase ion–molecule reactions of α,α,α′,α′ tetrafluorodimethyl ether both alone and in mixtures with water have been examined. The dominant feature of the ion chemistry of these mixtures is the sequential bimolecular production of the hydrated hydronium ion, H5O2+. Two independent mechanistic pathways for production of H5O2+ are outlined arising from reaction of H3O+ with (CF2H)2O and from CF2H—O=CHF+ with H2O. Implications for examination of solvent switching equilibria are discussed.

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