DFT study of electronic properties, structure and spectra of aryl diazonium cations

Minaev, B. F.; Bondarchuk, Sergey V.; Gîrţu, Mihai A.

doi:10.1016/j.theochem.2009.02.022

Cited by 21 publications

(25 citation statements)

References 35 publications

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“…As a result, a shift of +9 cm -1 of the N≡N vibration mode was found for DS-COOH relative to DS. The electron-withdrawing groups (i.e., COOH) induce an increase of the contribution of a structure like and hence induce a shift of the N≡N stretching vibration to higher wavenumbers [29,36]. This agrees with the N≡N bond-length decrease [36] and is also consistent with the polarizability increase of the N≡N bond.…”

Section: N≡n Group Vibrationssupporting

confidence: 58%

“…The electron-withdrawing groups (i.e., COOH) induce an increase of the contribution of a structure like and hence induce a shift of the N≡N stretching vibration to higher wavenumbers [29,36]. This agrees with the N≡N bond-length decrease [36] and is also consistent with the polarizability increase of the N≡N bond. Experimental data show in fact that the relative intensity of the N≡N bond is increased by 23% for DS-COOH compared with that obtained for DS, DS-C 10 H 21 and DS-CH 2 CH 2 NH 2 ( Figure S2 and …”

Section: N≡n Group Vibrationssupporting

confidence: 58%

“…According to the literature [29,36], the position of the N≡N vibration mode depends upon the nature of the ring substituent located in the para-position of a diazonium salt. Our results show that substituents have a rather low effect on the N≡N fragment following the observed wavenumber shifts (Table 1; Figure S2 in Supporting Information).…”

Section: N≡n Group Vibrationsmentioning

confidence: 99%

See 2 more Smart Citations

Raman Characterization of Phenyl-Derivatives: From Primary Amine to Diazonium Salts

Betelu¹,

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Boubekeur-Lecaque³

et al. 2017

J Org Inorg Chem

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Section: N≡n Group Vibrationssupporting

confidence: 58%

Section: N≡n Group Vibrationssupporting

confidence: 58%

Section: N≡n Group Vibrationsmentioning

confidence: 99%

See 1 more Smart Citation

Raman Characterization of Phenyl-Derivatives: From Primary Amine to Diazonium Salts

Betelu¹,

Tijunelyte²,

Boubekeur-Lecaque³

et al. 2017

J Org Inorg Chem

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“…The reactivity of the BBC compounds can be dependent on the spin multiplicity changes during the reaction. [71][72][73] The peculiarities of the Bzd 2+ dication reactivity will be an issue of the further study.…”

Section: Discussionmentioning

confidence: 99%

Electronic descriptors for analytical use of the benzidine‐based compounds and the mechanism of oxidative coupling of anilines

Bondarchuk

Minaev

2014

J of Physical Organic Chem

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A number of hybrid exchange-correlation functionals, namely, B3LYP, BMK, M06-2X, PBE0, CAM-B3LYP, BH&HLYP, and HSE06, have been employed to calculate the electronic spectra of a series of the N,N′-derivatives of benzidine, their radical cations, and dications; the results are compared with available experimental data. In most cases studied, the timedependent density functional theory results based on the CAM-B3LYP and BMK functionals indicate a better agreement with the experimental absorption bands in the UV-Vis spectra. The other five functionals provide statistically comparable but lower accuracy. On the basis of the time-dependent density functional theory calculations with both the CAM-B3LYP and BMK functionals and the 6-311 + G(d,p) basis set including effect of polar medium simulation, the electronic spectrum of the benzidine dication has been completely assigned. Because the latter dication is formed during oxidative coupling of two aniline molecules, as the reductive reagents for analytical determination of strong oxidants, the mechanism of this reaction has been clarified on the ground of density functional theory calculations including effect of dispersion for all possible reaction paths and intermediates. By the analysis of spectral properties and ionization energies of several aniline derivatives, a few simple electronic descriptors that help to justify a reagent molecule as a potentially favorable for colorimetric use have been proposed.

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“…Earlier we have found that the aryl diazonium cations can not decompose via a simple reduction into the corresponding aryl diazenyl radical during the Meerwein reaction [34,35]. These cations must be excited first to the triplet state which is rather unstable with respect to the C-N bond cleavage and resulting in the subsequent nitrogen loss and the triplet aryl cations formation.…”

Section: Obtained Correlationsmentioning

confidence: 95%

About possibility of the triplet mechanism of the Meerwein reaction

Bondarchuk

Minaev

2010

Journal of Molecular Structure: THEOCHEM

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DFT study of electronic properties, structure and spectra of aryl diazonium cations

Cited by 21 publications

References 35 publications

Raman Characterization of Phenyl-Derivatives: From Primary Amine to Diazonium Salts

Raman Characterization of Phenyl-Derivatives: From Primary Amine to Diazonium Salts

Electronic descriptors for analytical use of the benzidine‐based compounds and the mechanism of oxidative coupling of anilines

About possibility of the triplet mechanism of the Meerwein reaction

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