Two P, Ten P, White P, Red P: Mechanistic Exploration of the Oligomerization of Red Phosphorus from Diphosphorus with the Ab Initio Nanoreactor.
Inorg Chem
; 2024 Oct 01.
Article
em En
| MEDLINE
| ID: mdl-39352782
ABSTRACT
Phosphorus is critical to humans on many fronts, yet we do not have a mechanistic understanding of some of its most basic transformations and reactionsânamely the oligomerization of white phosphorus to red. With heat or under ultraviolet (UV) exposure, it has been experimentally demonstrated that white phosphorus dissociates into diphosphorus units which readily form red phosphorus. However, the mechanism of this process is unknown. The ab initio nanoreactor approach was used to explore the potential energy surface of phosphorus clusters. Density functional theory and metadynamics simulations were used to characterize potential reaction pathways. A mechanism for oligomerization is proposed to take place via diphosphorus additions at π-bonds and weak σ-bonds through three membered ring intermediates. Downhill paths through P6 and P8 clusters eventually result in P10 clusters that can oligomerize into red phosphorus chains. The initial, rate limiting step for this process has an energy barrier of 24.2 kcal/mol.
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Bases de dados:
MEDLINE
Idioma:
En
Revista:
Inorg Chem
Ano de publicação:
2024
Tipo de documento:
Article
País de afiliação:
Estados Unidos