Catalogo Articoli (Spogli Riviste)

OPAC HELP

Titolo:
Fluorinated methyl cation (CF3+, CFH2+)-alkyl nitrile cluster ions
Autore:
Alvarez, J; Denault, JW; Cooks, RG;
Indirizzi:
Purdue Univ, Dept Chem, W Lafayette, IN 47906 USA Purdue Univ W LafayetteIN USA 47906 Dept Chem, W Lafayette, IN 47906 USA
Titolo Testata:
JOURNAL OF MASS SPECTROMETRY
fascicolo: 12, volume: 35, anno: 2000,
pagine: 1407 - 1415
SICI:
1076-5174(200012)35:12<1407:FMC(CN>2.0.ZU;2-3
Fonte:
ISI
Lingua:
ENG
Soggetto:
NUCLEOPHILIC DISPLACEMENT-REACTIONS; MS(3) MASS-SPECTROMETRY; GAS-PHASE; KINETIC METHOD; SN2 REACTIONS; THERMOCHEMICAL DETERMINATIONS; S(N)2 REACTIONS; TEMPERATURE-DEPENDENCE; TRANSITION STRUCTURES; ACTIVATION-ENERGIES;
Keywords:
ion structure; ab initio calculations; methyl cation affinity; thermochemistry; RRK calculations;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Life Sciences
Physical, Chemical & Earth Sciences
Citazioni:
74
Recensione:
Indirizzi per estratti:
Indirizzo: Cooks, RG Purdue Univ, Dept Chem, W Lafayette, IN 47906 USA Purdue Univ WLafayette IN USA 47906 W Lafayette, IN 47906 USA
Citazione:
J. Alvarez et al., "Fluorinated methyl cation (CF3+, CFH2+)-alkyl nitrile cluster ions", J MASS SPEC, 35(12), 2000, pp. 1407-1415

Abstract

Ion-molecule reactions of CF3+ or CFH2+ with an acetonitrile-butyronitrilemixture yield product cluster ions in which the two neutral molecules are associated with the cation, The structures of the ion-molecule product ionswere investigated by collision-induced dissociation in a multi-quadrupole mass spectrometer, The cluster ions fragment by loss of one neutral alkyl nitrile, The abundance of the fragment ions shows an unexpected inverse correlation with the proton affinity of the alkyl nitrile, This result is inconsistent with the formation of a simple cation-bound dimeric cluster containing two alkyl nitrile molecules and a fluorinated methyl cation; instead, apair of non-symmetrical dimeric complexes, separated by a large internal barrier, is indicated. This result is analogous to that observed for the putative methyl cation-bound heterodimer of acetonitrile and butyronitrile, Collision energy dependence studies and ab initio calculations suggest that the dimeric complexes are formed in potential energy wells located in an approximately symmetrical potential energy surface. Quasiequilibrium theory calculations were used in order to obtain additional insights into the experimental data. Copyright (C) 2000 John Wiley & Sons, Ltd.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 10/07/20 alle ore 02:49:03