Interaction of metal cations with alkylnitriles in the gas phase: solvation of metal ions by the hydrocarbon chain.
Eur J Mass Spectrom (Chichester)
; 21(3): 579-87, 2015.
Article
en En
| MEDLINE
| ID: mdl-26307737
ABSTRACT
Relative affinity measurements of monovalent metal ions (M = Li(+), Na(+), Cu(+)and Ag(+)) toward aliphatic nitriles have been performed using the kinetic method by dissociation of metal bound dimer ions of the type R1C≡N-M(+)-N≡CR(2). It is found, particularly for Cu(+) and Ag(+), that the affinity towards nitriles having long chains (>C(6)) is markedly enhanced. This is attributed to a bidentate interaction of the metal ion with the nitrile moiety and the aliphatic chain. Theoretical calculations on the copper complexes show that these bidentate structures enjoy about 30% greater copper ion affinities compared to their linear counterparts. Such aliphatic interactions also play a major role in the dissociation chemistry of copper bound tetramers of the kind (RC≡N)(4)Cu(2+â) where the long aliphatic chain R curls around the copper ion to facilitate electron transfer or a redox reaction to produce (RC≡N)(2)Cu(+) + RC≡N(+â) + RC≡N.
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Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
Eur J Mass Spectrom (Chichester)
Año:
2015
Tipo del documento:
Article
País de afiliación:
Canadá