TY - JOUR
T1 - The question of tautomerism of alkylnitrile and isonitrile radical cations
AU - Chess, Edward K.
AU - Lapp, R. L.
AU - Gross, Michael L.
PY - 1982/10
Y1 - 1982/10
N2 - The isomeric pairs [CH3CN]+˙ and [CH2CNH]+˙ and [CH3NC]+˙ and [CH2NCH]+˙ have been established as stable, noninterconverting structures. The conclusion derives from studies of collision induced decomposition spectra. The same conclusion pertains for the ions [CH3CH2CN]+˙ and [CH3CHCNH]+˙, and for [NCCH2CH2CN]+˙, [HNCCHCH2CN]+˙ and [HNCCHCHCNH]+˙. The energy barrier of a [1,3]‐hydrogen shift, a possible isomerization mechanism, is determined to be at least 163 kJ mol−1 for the [CH3CN]+˙ and [CH2CNH]+˙ pair, and the barrier may be as high as 318 kJ mol−1. The C3H5N and C4H4N2 radical cations decompose before they can be activated with 318 kJ mol−1 of internal energy.
AB - The isomeric pairs [CH3CN]+˙ and [CH2CNH]+˙ and [CH3NC]+˙ and [CH2NCH]+˙ have been established as stable, noninterconverting structures. The conclusion derives from studies of collision induced decomposition spectra. The same conclusion pertains for the ions [CH3CH2CN]+˙ and [CH3CHCNH]+˙, and for [NCCH2CH2CN]+˙, [HNCCHCH2CN]+˙ and [HNCCHCHCNH]+˙. The energy barrier of a [1,3]‐hydrogen shift, a possible isomerization mechanism, is determined to be at least 163 kJ mol−1 for the [CH3CN]+˙ and [CH2CNH]+˙ pair, and the barrier may be as high as 318 kJ mol−1. The C3H5N and C4H4N2 radical cations decompose before they can be activated with 318 kJ mol−1 of internal energy.
UR - http://www.scopus.com/inward/record.url?scp=84989092466&partnerID=8YFLogxK
U2 - 10.1002/oms.1210171005
DO - 10.1002/oms.1210171005
M3 - Article
AN - SCOPUS:84989092466
SN - 0030-493X
VL - 17
SP - 475
EP - 480
JO - Organic Mass Spectrometry
JF - Organic Mass Spectrometry
IS - 10
ER -