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Title: Gas-phase reactions of fullerene monocations, dications, and trications with nitriles

Abstract

Results are reported for the reactions of the fullerene ions C[sub 60[center dot]+], C[sub 70[center dot]+], C[sub 60][sup 2+], C[sub 70][sup 2+], and C[sub 60[center dot]3+] with the nitriles HCN, CH[sub 3]CN, CH[sub 2]CHCN, CH[sub 3]CH[sub 2]CN, CH[sub 2]CHCH[sub 2]CN, CH[sub 3]CH[sub 2]CH[sub 2]CN, (CH[sub 3])[sub 2]CHCN, C[sub 2]N[sub 2], and CH[sub 2](CN)[sub 2]. The reactions were studied using a selected-ion flow tube (SIFT) at 294 [+-] 2 K and a helium buffer gas pressure of 0.35 [+-] 0.01 Torr and exhibited a wide range of chemical behavior. For the monocations C[sub 60][sup [center dot]+] and C[sub 70][sup [center dot]+], no detectable reaction occurred with any of the nitriles. For the dications C[sub 60][sup 2+], and C[sub 70][sup 2+], the only primary or secondary product channel evident in all instances was addition: tertiary association was seen to be considerably less efficient than the primary and secondary reactions, and the formation of a quadruple adduct C[sub 60](RCN)[sub 4][sup 2+] was only detected in the reaction with butyronitrile, CH[sub 3]CH[sub 2]CH[sub 2]CN. The observed primary rate coefficients show a very clear dependence upon the molecular complexity of the nitrile: association proceeds more efficiently for nitriles with a higher number of hydrogen atoms.more » This observation is explained in terms of a model which relates the number of C-H bonds - or, alternatively, the number of internal rotational modes - in the collision complex to the lifetime and probability of stabilization of this complex. 42 refs., 5 figs., 3 tabs.« less

Authors:
; ; ; ;  [1]
  1. York Univ., North York, Ontario (Canada)
Publication Date:
OSTI Identifier:
5067113
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society; (United States)
Additional Journal Information:
Journal Volume: 115:21; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; CATIONS; CHEMICAL REACTIONS; FULLERENES; NITRILES; ACETONITRILE; ACRYLONITRILE; EXPERIMENTAL DATA; HELIUM; HYDROCYANIC ACID; INTERSTELLAR SPACE; REACTION KINETICS; THEORETICAL DATA; VAPORS; CARBON; CHARGED PARTICLES; CYANIDES; DATA; ELEMENTS; FLUIDS; GASES; HYDROGEN COMPOUNDS; INFORMATION; INORGANIC ACIDS; IONS; KINETICS; NONMETALS; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; RARE GASES; SPACE; 400201* - Chemical & Physicochemical Properties; 360601 - Other Materials- Preparation & Manufacture

Citation Formats

Javahery, G, Petrie, S, Wang, J, Wincel, H, and Bohme, D K. Gas-phase reactions of fullerene monocations, dications, and trications with nitriles. United States: N. p., 1993. Web. doi:10.1021/ja00074a041.
Javahery, G, Petrie, S, Wang, J, Wincel, H, & Bohme, D K. Gas-phase reactions of fullerene monocations, dications, and trications with nitriles. United States. https://doi.org/10.1021/ja00074a041
Javahery, G, Petrie, S, Wang, J, Wincel, H, and Bohme, D K. Wed . "Gas-phase reactions of fullerene monocations, dications, and trications with nitriles". United States. https://doi.org/10.1021/ja00074a041.
@article{osti_5067113,
title = {Gas-phase reactions of fullerene monocations, dications, and trications with nitriles},
author = {Javahery, G and Petrie, S and Wang, J and Wincel, H and Bohme, D K},
abstractNote = {Results are reported for the reactions of the fullerene ions C[sub 60[center dot]+], C[sub 70[center dot]+], C[sub 60][sup 2+], C[sub 70][sup 2+], and C[sub 60[center dot]3+] with the nitriles HCN, CH[sub 3]CN, CH[sub 2]CHCN, CH[sub 3]CH[sub 2]CN, CH[sub 2]CHCH[sub 2]CN, CH[sub 3]CH[sub 2]CH[sub 2]CN, (CH[sub 3])[sub 2]CHCN, C[sub 2]N[sub 2], and CH[sub 2](CN)[sub 2]. The reactions were studied using a selected-ion flow tube (SIFT) at 294 [+-] 2 K and a helium buffer gas pressure of 0.35 [+-] 0.01 Torr and exhibited a wide range of chemical behavior. For the monocations C[sub 60][sup [center dot]+] and C[sub 70][sup [center dot]+], no detectable reaction occurred with any of the nitriles. For the dications C[sub 60][sup 2+], and C[sub 70][sup 2+], the only primary or secondary product channel evident in all instances was addition: tertiary association was seen to be considerably less efficient than the primary and secondary reactions, and the formation of a quadruple adduct C[sub 60](RCN)[sub 4][sup 2+] was only detected in the reaction with butyronitrile, CH[sub 3]CH[sub 2]CH[sub 2]CN. The observed primary rate coefficients show a very clear dependence upon the molecular complexity of the nitrile: association proceeds more efficiently for nitriles with a higher number of hydrogen atoms. This observation is explained in terms of a model which relates the number of C-H bonds - or, alternatively, the number of internal rotational modes - in the collision complex to the lifetime and probability of stabilization of this complex. 42 refs., 5 figs., 3 tabs.},
doi = {10.1021/ja00074a041},
url = {https://www.osti.gov/biblio/5067113}, journal = {Journal of the American Chemical Society; (United States)},
issn = {0002-7863},
number = ,
volume = 115:21,
place = {United States},
year = {1993},
month = {10}
}