Theoretical study of the triplet state aryl cations recombination: A possible route to unusually stable doubly charged biphenyl cations

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 syst...

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Bibliographic Details
Published in:	International journal of quantum chemistry Vol. 113; no. 24; pp. 2580 - 2588
Main Authors:	Bondarchuk, Sergey V., Minaev, Boris F., Fesak, Alexander Yu
Format:	Journal Article
Language:	English
Published:	Hoboken Blackwell Publishing Ltd 15-12-2013 Wiley Subscription Services, Inc
Subjects:	aryl cation Aryl cations biphenyl derivative Biphenyl derivatives Chemistry Condensed matter physics Dications Molecular physics organic dication Physical chemistry Positive ions Quantum chemistry Quantum physics self-recombination triplet state
Online Access:	Get full text
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Summary:	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. The chemical reactivity of diamagnetic molecules is largely determined by the properties of their triplet excited states rather than their closed‐shell ground singlet state. As an example of this type of “spin‐catalysis,” the self‐recombination reaction of the triplet state 4‐aminophenyl cations leads to the formation of the benzidine dication. The corresponding transition state is “reactant‐like” and located at the CipsoCipso interatomic distance of 4.0 Å.
Bibliography:	ark:/67375/WNG-HJ1VXKN4-B Ministry of Education and Science of Ukraine, Research Fund - No. 0109U0002547 istex:7EA8BBB8099FA2C5D2CF8C64E8D518A995CB398F ArticleID:QUA24509
ISSN:	0020-7608 1097-461X 1097-461X
DOI:	10.1002/qua.24509