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Density functional study of ortho-substituted phenyl cations in polar medium and in the gas phase
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512).
2011 (English)In: Chemical Physics, ISSN 0301-0104, E-ISSN 1873-4421, Vol. 389, no 1-3, 68-74 p.Article in journal (Refereed) Published
Abstract [en]

Density functional theory (DFT) calculations of several 2-X-substituted phenyl cations (X = 2-CHO, 2-CH(2)OH, 2-CHS, 2-CH=NH, 2-OCH=NH, 2-SCH=NH, 2-CH=CH-CH=CH(2), 2-CH=CH(2) and 2-NO(2)) have been carried out in the gas phase and in acetonitrile (MeCN) at the B3LYP/6-31G(d,p) level of theory. The stationary point geometry of these aryl cations have been found to be in strong dependency of the medium. In the gas phase, unexpected behavior of considered aryl cations takes place resulting in the rearrangement or ring closure reaction. Such the cyclization reaction is proceeding via the nearby atom of the substituent which appears in relative vicinity (up to similar to 3 angstrom) to the cationic center. Only in the case of 2-NO(2) derivative, the geometry optimization has lead to rearranged quazi-quinoid structure of the cation that, obviously, takes place because of instability of the ring formed. Scan of the potential energy surface (PES) of 2-nitrophenyl cation has displayed no any reaction path leading toward the rearranged structure. Thus, the impossibility of existing of the singlet state of 2-nitrophenyl cation in the gas phase has been offered. The singlet-triplet transition of 2-nitrophenyl cation has been discussed in terms of the spin-orbit coupling (SOC) effects.

Place, publisher, year, edition, pages
2011. Vol. 389, no 1-3, 68-74 p.
Keyword [en]
Aryl cations, Ring closure, Triplet state, Density functional theory, Spin-orbit coupling
National Category
Physical Sciences Chemical Sciences
URN: urn:nbn:se:kth:diva-51415DOI: 10.1016/j.chemphys.2011.08.005ISI: 000296760800008ScopusID: 2-s2.0-84962360738OAI: diva2:464527
QC 20111213Available from: 2011-12-13 Created: 2011-12-12 Last updated: 2011-12-13Bibliographically approved

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Minaev, Boris F.
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