Gas phase ion-molecule reactions of alkyl nitrites by ion cyclotron resonance spectroscopy

1978 ◽  
Vol 27 (2) ◽  
pp. 163-183 ◽  
Author(s):  
R. Farid ◽  
T.B. McMahon
1985 ◽  
Vol 63 (2) ◽  
pp. 281-287 ◽  
Author(s):  
O. Elsenstein ◽  
M. Kayser ◽  
M. Roy ◽  
T. B. McMahon

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.


1980 ◽  
Vol 58 (8) ◽  
pp. 863-865 ◽  
Author(s):  
R. L. Clair ◽  
T. B. McMahon

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.


1978 ◽  
Vol 56 (5) ◽  
pp. 670-679 ◽  
Author(s):  
T. B. McMahon

A number of gas phase ion molecule reactions of protonated species with acyl halides have been examined by ion cyclotron resonance spectroscopy. A number of these reactions are found to involve an addition–elimination reaction having the character of an acidic solvolysis process. Observation of the occurrence or non-occurrence of such reactions and a consideration of appropriate thermochemical data allow a set of criteria to be formulated governing the feasibility of observing the acidic solvolysis reaction. In addition a number of mechanistic inferences are made concerning intermediates involved in the various reactions.


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