Features of the decomposition of the nitrosyl iron complex with thiourea ligands under aerobic conditions: experiment and kinetic and quantum chemical modeling

Pokidova, O. V.; Psikha, B. L.; Emel’yanova, N. S.; Gutsev, Lavrenty G.; Novikova, V. O.; Zagainova, E. A.; Санина, Н. А.

doi:10.1007/s11172-022-3569-0

Cited by 7 publications

(2 citation statements)

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“…As shown earlier [43], the formation of nitrates was recorded in aerobic aqueous solutions of complex 1. At the same time, an assumption was made about the possible mechanisms of such processes.…”

Section: No 3releasesupporting

confidence: 54%

“…Its detachment requires significant (31.7 kcal/mol) energy. However, earlier calculations were carried out [20,35,42,43], showing that intramolecular oxidation of NO ligands can occur in DNIC under aerobic conditions, and, at the same time, NO2 is rather easily released. Figure 5 shows another scheme, in which the initial complex adds one water molecule, passing into complex 8, and an oxygen molecule adds at the Fe-N bond [20,36] to form complex 9.…”

Section: No 2 Releasementioning

confidence: 98%

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Quantum-chemical modeling of NO ligand activity in cationic nitrosyl iron complex [Fe(SC (NH2)2)2(NO)2]+ occurring in aerobic aqueous conditions

Gutsev

Emel’yanova

Pokidova

et al. 2023

Preprint

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The chemical reaction of a cationic ironnitrosyl complex with thiourea ligands of the composition [Fe(SC(NH2)2)2(NO)2]+ in aerobic aqueous conditions was studied via kinetic and quantum chemical modeling. An implicit expression is found for the kinetic curve which describes this process. The mechanism of interaction of the complex with molecular oxygen in the presence of water molecules was studied with density functional method. An optimized geometry of the initial, final, intermediate and transition states were obtained and the, energy profiles of the reactions were constructed. It was shown that the explicit inclusion of the water molecules in the reaction of the interaction of the complex with oxygen and the further transformation of the resulting products demonstrated not only the mechanism of the NO release, but also the intramolecular transformation of NO into NO2, NO2−, NO3−, ONOO−. A mechanism was proposed for the formation of a OH radical in the system and its release, along with the previously mentioned products, into solution.

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Section: No 3releasesupporting

confidence: 54%