10.1021/jo061204m.s001
Yang-Ping Liu
Yang-Ping
Liu
Lan-Fen Wang
Lan-Fen
Wang
Zhou Nie
Zhou
Nie
Yi-Qiong Ji
Yi-Qiong
Ji
Yang Liu
Yang
Liu
Ke-Jian Liu
Ke-Jian
Liu
Qiu Tian
Qiu
Tian
Effect of the Phosphoryl Substituent in the Linear Nitrone on the
Spin Trapping of Superoxide Radical and the Stability of the
Superoxide Adduct: Combined Experimental and
Theoretical Studies
American Chemical Society
2006
decay
superoxide
phosphoryl group
intramolecular
Superoxide
B 3LYP level
HOPPN
PBN
adduct
DFT
phosphorylated
calculation
2006-09-29 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/Effect_of_the_Phosphoryl_Substituent_in_the_Linear_Nitrone_on_the_Spin_Trapping_of_Superoxide_Radical_and_the_Stability_of_the_Superoxide_Adduct_Combined_Experimental_and_Theoretical_Studies/3056785
A new phosphorylated linear nitrone <i>N</i>-(4-hydroxybenzyliene)-1-diethoxyphosphoryl-1-methylethylamine
<i>N</i>-oxide (4-HOPPN) was synthesized, and its X-ray structure was determined. The spin trapping ability
of various kinds of free radicals by 4-HOPPN was evaluated. Kinetic study of decay of the superoxide
spin adduct (4-HOPPN-OOH) shows the half-life time of 8.8 min. On the basis of the X-ray structural
coordinates, theoretical analyses using density functional theory (DFT) calculations at the B3LYP/6-31+G(d,p)//B3LYP/6-31G(d) level were performed on spin-trapping reactions of superoxide radical with
4-HOPPN and PBN and three possible decay routes for their corresponding superoxide adducts. The
comparative calculations on the spin-trapping reactions with superoxide radical predicted that both spin
traps share an identical reaction type and have comparable potency when spin trapping superoxide radical.
Analysis of the optimized geometries of 4-HOPPN-OOH and PBN-OOH reveals that an introduction of
the phosphoryl group can efficiently stabilize the spin adduct through the intramolecular H-bonds, the
intramolecular nonbonding attractive interactions, as well as the bulky steric protection. Examination of
the decomposition thermodynamics of 4-HOPPN-OOH and PBN-OOH further supports the stabilizing
role of the phosphoryl group to a linear phosphorylated spin adduct.