Synthesis, Characterization, and Structures of a Persistent Aniline Radical Cation

Chen, Xiaoyu; Wang, Xingyong; Sui, Yunxia; Li, Yi‐Zhi; Ma, Jing; Zuo, Jing‐Lin; Wang, Xinping

doi:10.1002/ange.201205478

Cited by 11 publications

(73 citation statements)

References 39 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…I thus suspect that the spectrum in Figure 2 of Ref. [1] is due to paramagnetic contaminations (in the lower percentage range) incorporated in a diamagnetic, that is, ESR-silent compound. An estimation of the spin concentration would have easily established this.…”

Section: Esr Spectrometrymentioning

confidence: 94%

“…[1]. Unfortunately, instrument settings were not given either in the paper or in its Supporting Information; thus, the choice of suitable recording conditions (especially microwave power and modulation amplitude) can only be assumed.…”

Section: Esr Spectrometrymentioning

confidence: 99%

“…The authors inferred their assignment of the ESR spectrum to TBAC + from a spectral simulation (Figure 2 of Ref. [1]) with hyperfine splitting constants (hfsc) of a( 14 N) = 5.48 G, a(N 1 H) = 6.62 G (2 H), and a( 1 H meta ) = 2.90 G (2 H). [3] Reference was given to a paper by Neugebauer et al where ESR data are reported for a variety of aniline radical cations, but not for TBAC + .…”

Section: Esr Spectrometrymentioning

confidence: 99%

“…Close inspection of the data presented in Ref. [1], however, casts serious doubts on the identification of the green solid as the stoichiometrically pure TBAC + SbF 6 À radical cation salt. Also, the interpretation of the temperature-dependent structural changes in terms of a Jahn-Teller distortion appears to be highly ambiguous.…”

mentioning

confidence: 94%

“…In their recent Communication, [1] Chen et al reported on the "Synthesis, Characterization, and Structures of a Persistent Aniline Radical Cation". After oxidation of 2,4,6-tri-tertbutylaniline (TBA) with AgSbF 6 in dichloromethane the authors isolated a green, crystalline compound which they identified, based on UV/Vis and ESR spectrometric data, as the hexafluoroantimonate salt of the TBA radical cation, TBAC + SbF 6 À (1) (Scheme 1).…”

mentioning

confidence: 99%

See 4 more Smart Citations

Comment on “Synthesis, Characterization, and Structures of a Persistent Aniline Radical Cation”: A New Interpretation Is Necessary

Korth¹

2013

Angewandte Chemie

View full text Add to dashboard Cite

Das Anilin‐Radikalkation unter nochmaliger Prüfung: Der Autor dieser Korrespondenz argumentiert, dass die 2012 mitgeteilten spektrometrischen Daten für 2,4,6‐Tri‐tert‐butylanilin (TBA) keinem stöchiometrisch reinen TBA.+SbF6−‐Salz entsprechen, die quantenchemischen Daten die berichteten Strukturdaten nicht stützen und die temperaturabhängigen Strukturänderungen auch durch andere Ursachen als den Jahn‐Teller‐Effekt interpretierbar sind.

show abstract

Section: Esr Spectrometrymentioning

confidence: 94%

Section: Esr Spectrometrymentioning

confidence: 99%

Section: Esr Spectrometrymentioning

confidence: 99%

mentioning

confidence: 94%

mentioning

confidence: 99%

See 3 more Smart Citations

Comment on “Synthesis, Characterization, and Structures of a Persistent Aniline Radical Cation”: A New Interpretation Is Necessary

Korth¹

2013

Angewandte Chemie

View full text Add to dashboard Cite

show abstract

Comment on “Synthesis, Characterization, and Structures of Persistent Aniline Radical Cation”: It Is a Protonated Aniline and Not an Aniline Radical Cation

et al. 2013

View full text Add to dashboard Cite

anilines · Jahn-Teller effect · radical cations · spin contaminationIn a recent publication, [1] Chen et al. have claimed the isolation of a persistent radical-cation salt derived from 2,4,6tri-tert-butylaniline (TBA) by its prolonged ( % 24 h) reaction with equimolar AgSbF 6 in dichloromethane at ambient temperatures with > 80 % yield. They have determined the structure of this radical-cation salt by single-crystal X-ray crystallography at 123 K (À150 8C) and found that this radical cation exhibits a long C Ar À N bond length of 1.496 . They have also claimed that the aromatic ring in the crystalline radical cation undergoes a temperature-dependent transformation from a bisallyl to a quinoidal geometry, while the C Ar ÀN bond length remained largely unaffected (see structures below).This highly unusual crystallographic observation in TBA + C was reconciled by ab initio calculations using an unrestricted MP2 method. Based on our extensive experience with organic cation radicals, [2] this finding was highly troubling because of the lack of involvement of the nitrogen lone pair in stabilizing the cationic aryl group (i.e. long C Ar ÀN bond) and the fact that the electronic reorganization of aromatic ring required such high temperatures (i.e. + 100 8C).In order to understand this highly unusual finding, we have redetermined the single-crystal X-ray structure of this supposed TBA salt at different temperatures and now unequivocally show that it is protonated aniline and not an aniline radical cation. Below, we carefully outline various experimental and computational missteps that led these authors [1] to incorrectly identify this salt.

show abstract

Reply to Comments on “Synthesis, Characterization, and Structures of Persistent Aniline Radical Cation”

et al. 2013

Self Cite

View full text Add to dashboard Cite

Die Identifizierung des Anilin‐Radikalkations TBA.+ (TBA=2,4,6‐tBu3C6H2NH2), über die 2012 berichtet wurde, wird in den beiden vorhergehenden Korrespondenzartikeln angezweifelt. Die Autoren der ursprünglichen Veröffentlichung haben ihre UV/Vis‐ und EPR‐Daten nochmals überprüft und insistieren, dass das TBA.+‐Radikalkation tatsächlich beständig und stabil ist. Die mögliche Kokristallisation von TBA.+ mit TBAH+ bewirkt eine Verkomplizierung der Kristallstruktur.

show abstract

Synthesis, Characterization, and Structures of a Persistent Aniline Radical Cation

Cited by 11 publications

References 39 publications

Comment on “Synthesis, Characterization, and Structures of a Persistent Aniline Radical Cation”: A New Interpretation Is Necessary

Comment on “Synthesis, Characterization, and Structures of a Persistent Aniline Radical Cation”: A New Interpretation Is Necessary

Comment on “Synthesis, Characterization, and Structures of Persistent Aniline Radical Cation”: It Is a Protonated Aniline and Not an Aniline Radical Cation

Reply to Comments on “Synthesis, Characterization, and Structures of Persistent Aniline Radical Cation”

Contact Info

Product

Resources

About