The question of tautomerism of alkylnitrile and isonitrile radical cations

Edward K. Chess; R. L. Lapp; Michael L. Gross

doi:10.1002/oms.1210171005

The question of tautomerism of alkylnitrile and isonitrile radical cations

Edward K. Chess
, R. L. Lapp
, Michael L. Gross

Research output: Contribution to journal › Article › peer-review

25 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	475-480
Number of pages	6
Journal	Organic Mass Spectrometry
Volume	17
Issue number	10
DOIs	https://doi.org/10.1002/oms.1210171005
State	Published - Oct 1982

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title = "The question of tautomerism of alkylnitrile and isonitrile radical cations",

abstract = "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.",

author = "Chess, \{Edward K.\} and Lapp, \{R. L.\} and Gross, \{Michael L.\}",

year = "1982",

month = oct,

doi = "10.1002/oms.1210171005",

language = "English",

volume = "17",

pages = "475--480",

journal = "Organic Mass Spectrometry",

issn = "0030-493X",

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}

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 - https://www.scopus.com/pages/publications/84989092466

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 -

The question of tautomerism of alkylnitrile and isonitrile radical cations

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