Structure of the 1,3-dinitrobenzene dianion studied by multiconfigurational methods

Михайлов, М. Н.; Mendkovich, A. S.; Kuz’minskii, M. B.; Русаков, А. И.

doi:10.1007/s11172-007-0222-x

Russ Chem Bull

2007

DOI: 10.1007/s11172-007-0222-x

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Structure of the 1,3-dinitrobenzene dianion studied by multiconfigurational methods

М. Н. Михайлов

A. S. Mendkovich

M. B. Kuz’minskii

et al.

Abstract: The structure of the 1,3 dinitrobenzene dianion in the ground and lowest excited electron states was studied by quantum chemical methods. The dianion, unlike the radical anion, is characterized by the symmetrical structure in both the ground triplet ( 3 B 1 ) and lowest excited singlet ( 1 A 1 ) states. The wave function of the singlet state has the biradical character to a great extent. The singlet triplet splitting calculated by the CASSCF and MRMP2 methods is 6 and 2 kcal mol -1 , respectively.

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“…2 The one electron transfer products, viz., radical an ions, are the objects of investigation in the most part of theoretical 2 and experimental 3,4 works studying this re action. At the same time, as we have shown earlier 5, 6 for the 1,3 dinitrobenzene (1) radical anion and dianion, their electronic structures can substantially differ.…”

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Protonation of 1,3- and 1,4-dinitrobenzene dianions

et al. 2008

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The protonation of the electrochemically generated (0.1 М solution of tetrabutylammonium perchlorate in DMF) 1,3 dinitrobenzene (1) dianions with phenol, ethanol, tert butanol, and 1 butyl 3 methylimidazolium cation was studied by cyclic voltammetry and chronoamperometry at the carbositall working electrode. The rate constants for the protonation (k) of the dianion of compound 1 by phenol, 1 butyl 3 methylimidazolium cation, ethanol, and tert butanol were estimated by the comparison of the data of cyclic voltammetry and chronoamperometry with the digital simulation results, being 100, 50, 1.5, and 0.01 L mol -1 s -1 , respectively. The similarly obtained k value for the protonation of the dianion of 1,4 dinitrobenzene (2) with phenol is 13 L mol -1 s -1 . According to the quantum chemical calculation results, the protonation of the dianions of compounds 1 and 2 with phenol and 1 butyl 3 methylimidazolium cation can be classified as orbital controlled reactions.The electrochemical reduction (ER) of organic com pounds in aprotic solvents in the presence of proton do nors proceeds, as a rule, via the ECE mechanism, 1 whose key step is the protonation of negatively charged species formed due to the heterogeneous electron transfer to a substrate molecule. The rate and regioselectivity of protonation of such species are determined, in turn, by the electron density distribution on their frontier orbit als. 2 The one electron transfer products, viz., radical an ions, are the objects of investigation in the most part of theoretical 2 and experimental 3,4 works studying this re action. At the same time, as we have shown earlier 5,6 for the 1,3 dinitrobenzene (1) radical anion and dianion, their electronic structures can substantially differ.In this work, we studied the protonation of the dian ion of compound 1 with typical OH acids (phenol and aliphatic alcohols in DMF solutions in the presence of tetrabutylammonium perchlorate, 0.1 mol L -1 ) and CH acids (1 butyl 3 methylimidazolium tetrafluorobo rate). The 1 butyl 3 methylimidazolium cation (bmim + ) was chosen, because ionic liquids, particularly, those containing imidazolium cations, are often considered 7 in the electrochemistry of organic compounds as an alterna tive for traditional aprotic bipolar solvents. At the same time, it is known 8,9 that the bmim + cation can possess the proton donating properties due to the mobility of the hydrogen atom in the second position of the imid azole cycle. However, unambiguous proofs for the partic ipation of bmim + as a proton donor in the near electrode reactions were lacking to the recent time. When consider ing the effect of bmim + on the ER of dinitrobenzenes, only the formation of ion pairs of bmim + with the dianion of 1,4 dinitrobenzene (2) was mentioned, 10 and the inter action was so strong that resulted in the confluence of the potentials of the first and second steps. We showed 11 that the dianion of compound 1 was protonated with the bmim + cations.The behaviors of the dianions of compounds 1 and 2 in the presence o...

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Protonation of 1,3- and 1,4-dinitrobenzene dianions

et al. 2008

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Reactivity of Radical Anions and Dianions of Organic Compounds: A Review

Mendkovich,

Rusakov

2023

Russ J Electrochem

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Structure of the 1,3-dinitrobenzene dianion studied by multiconfigurational methods

Cited by 2 publications

References 4 publications

Protonation of 1,3- and 1,4-dinitrobenzene dianions

Protonation of 1,3- and 1,4-dinitrobenzene dianions

Reactivity of Radical Anions and Dianions of Organic Compounds: A Review

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