title: Thiol-induced nitric oxide donation mechanisms in substituted dinitrobenzofuroxans.
abstract: The goal of present work is the quantum chemical study of NO donation mechanism in dinitrobenzofuroxan aryl derivative. Mechanisms of its structural non-rigidity (1,3-N-oxidic and Boulton-Katritzky rearrangements) and minimum energy pathways of NO donation under the action of sulfanyl radical SH· were considered in details. DFT calculations were performed using B3LYP and UB3LYP functionals in the 6-311++G(d,p) basis set. Obtained results showed that a high experimentally proven NO-donor activity of dinitrobenzofuroxan aryl derivative is connected with its existence in the form of mixture of 1-N-oxide and 3-N-oxide, where the 3-N-oxide is more reactive towards SH·. The thiol-induced low-barrier mechanism of NO-donation is a result of para-aminophenyl substituent availability in position 7 of dinitrobenzofuroxan.
authors.affiliation: Department of Chemistry, Southern Federal University, 7, Zorge St., Rostov-on-Don, 344090, Russia.
authors.forename: Mikhail E
authors.initials: ME
authors.lastname: Kletskii
authors.affiliation: Department of Chemistry, Southern Federal University, 7, Zorge St., Rostov-on-Don, 344090, Russia. Electronic address: bboleg@gmail.com.
authors.forename: Oleg N
authors.initials: ON
authors.lastname: Burov
authors.affiliation: Department of Chemistry, Southern Federal University, 7, Zorge St., Rostov-on-Don, 344090, Russia.
authors.forename: Nikita S
authors.initials: NS
authors.lastname: Fedik
authors.affiliation: Department of Chemistry, Southern Federal University, 7, Zorge St., Rostov-on-Don, 344090, Russia.
authors.forename: Sergey V
authors.initials: SV
authors.lastname: Kurbatov
mesh_terms: D001583:Benzoxazoles / Q000737:chemistry*; D003198:Computer Simulation; D007536:Isomerism; D008956:Models, Chemical; D020030:Nitric Oxide Donors / Q000737:chemistry*; D009574:Nitro Compounds / Q000737:chemistry*; D011789:Quantum Theory; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D001583:Benzoxazoles; D020030:Nitric Oxide Donors; D009574:Nitro Compounds; D013438:Sulfhydryl Compounds
keywords: DFT calculations; Furoxan; Nitrogen(II) oxide; Thiol-induced NO donation mechanism