Hydrogen-Bonded Complexes of HPN⢠and HNP⢠Radicals with Carbon Monoxide.
Angew Chem Int Ed Engl
; : e202414456, 2024 Oct 04.
Article
em En
| MEDLINE
| ID: mdl-39365837
ABSTRACT
Phosphorus mononitride (PN) is a carrier of phosphorus in the interstellar medium. As the simplest derivatives of PN, the radical species HPN⢠and HNP⢠have remained elusive. Herein, we report the generation, characterization, and photochemistry of HPN⢠and HNP⢠in N2-matrix at 3 K. Specifically, HPN⢠was formed as a weakly bonded complex with CO in the matrix by 254 nm photolysis of the novel phosphinyl radical HPNCOâ¢. The â¢NPH-CO complex is extremely unstable, as it undergoes spontaneous isomerization to the lower-energy isomer â¢PNH-CO through fast quantum mechanical tunneling (QMT) with a half-life of 6.1 min at 3 K. Upon further irradiation at 254 nm, the reverse conversion of â¢PNH-CO to â¢NPH-CO along with dehydrogenation to yield PN was observed. The characterization â¢NPH-CO and â¢PNH-CO with matrix-isolation IR spectroscopy is supported by D, 15N, and 13C isotope labeling and quantum chemical calculations at the XYGJ-OS/AVTZ level of theory, and the mechanism by hydrogen atom tunneling is consistent with multidimensional instanton theory calculations.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
/
Angew. Chem. (Int. ed., Internet)
/
Angewandte Chemie (International ed. Internet)
Ano de publicação:
2024
Tipo de documento:
Article
País de afiliação:
China
País de publicação:
Alemanha