Hydrogen bond assisted reactions of carboxylic acids with alkyl halides in the gas phase by ion cyclotron resonance spectroscopy

1980 ◽  
Vol 58 (3) ◽  
pp. 307-309 ◽  
Author(s):  
R. L. Clair ◽  
T. B. McMahon
Keyword(s):  
Gas Phase ◽  
Cyclotron Resonance ◽  
Alkyl Halides ◽  
Nucleophilic Attack ◽  
Resonance Spectroscopy ◽  
Ion Cyclotron Resonance ◽  
Acid Solutions ◽  
Metal Fluorides ◽  
Ion Cyclotron ◽  
Alkyl Acetates

The reactions of the strongly hydrogen bonded anions, CH3CO2HF− and (CH3CO2)2H−, with alkyl halides have been studied in the gas phase by ion cyclotron resonance spectroscopy. A novel reaction of nucleophilic attack by (CH3CO2)2H− with alkyl chlorides to produce CH3CO2HCl− and alkyl acetates is reported. Parallels are drawn to synthetically important analogous reactions in glacial acetic acid solutions of alkali metal fluorides.

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.

Sign in / Sign up

Export Citation Format

Share Document