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Encapsulation and convex‐face thiozonolysis of triatomic sulfur (S 3 ) with carbon nanotubes
Author(s) -
Castillo Álvaro,
Lee Leda,
Greer Alexander
Publication year - 2012
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1866
Subject(s) - oniom , chemistry , carbon nanotube , nanotube , isomerization , density functional theory , molecule , computational chemistry , dipole , nanotechnology , organic chemistry , catalysis , materials science
Nanotubes are a class of host cavities increasingly used to encapsulate unstable molecules, yet none have been exploited to host reactive sulfur species, such as thiozone (S 3 ). In this paper, density functional theory and (ONIOM) calculations were used to compute single‐walled carbon nanotube (SWNT)–thiozone combinations for the inclusion of S 3 into the hollow nanotube space and to rationalize when 1,2,3‐thiozonide formation can take place. Nanotube diameter selectivity for the isomerization of the C 2v form of S 3 to the D 3h form proved to be elusive. Acyclic C 2v S 3 was ~6 kcal/mol more stable than cyclic D 3h S 3 whether it was free or encapsulated within an SWNT. 1,2,3‐Thiozonide formation took place on the convex side of nanotubes of low tube radii, such as the armchair (4,4) and (5,5) SWNTs. In terms of the reaction mode of C 2v S 3 , the 1,3‐dipolar addition reaction was preferred compared with the [2 + 2] cycloaddition and chelotrope paths. Copyright © 2011 John Wiley & Sons, Ltd.