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Theoretical study of the triplet state aryl cations recombination: A possible route to unusually stable doubly charged biphenyl cations
Author(s) -
Bondarchuk Sergey V.,
Minaev Boris F.,
Fesak Alexander Yu.
Publication year - 2013
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.24509
Subject(s) - chemistry , recombination , biphenyl , singlet state , aryl , density functional theory , triplet state , benzidine , spin states , photochemistry , ion , ground state , computational chemistry , excited state , atomic physics , inorganic chemistry , molecule , organic chemistry , physics , alkyl , biochemistry , gene
The self‐recombination reactions of 4‐aminophenyl cations and parent phenyl cations, each in ground triplet states, are studied within the framework of density functional theory. Only the total zero spin (singlet state) is chosen, as the quintet and triplet counterparts are nonreactive in these systems. The recombination products are the benzidine and biphenyl doubly charged cations. These species are unexpectedly stable. The transition state of the 4‐aminophenyl cations reaction is located at the distance of about 4.0 Å between the ipso‐carbon atoms. The activation barrier is predominantly formed by electrostatic repulsion between two cations and is estimated to be 27.6 kcal mol −1 [B3LYP/6–311+G( d , p )]. Similar results are obtained for the phenyl cations recombination. The general importance of the participation of other aryl cations in analogous organic reactions is discussed. © 2013 Wiley Periodicals, Inc.