Racemization mechanism of lithium tert-butylphenylphosphido-borane: A kinetic insight

The racemization mechanism of tert-butylphenylphosphido-borane is investigated experimentally and theoretically. Based on this converging approach, it is shown, first, that several phosphido-borane molecular species coexist at the time of the reaction and, second, that one particular of both initially assumed reactive routes most significantly contribute to the overall racemization process. From our converging modeling and experimental measurement, it comes out that the most probable species to be here encountered is a phosphido-borane-Li (THF)2 neutral solvate, whose P-stereogenic center monomolecular inversion through a Y-shaped transition structure (ΔrG°≠: 81 kJ mol−1) brings the largest contribution to the racemization process.

Références

Titre
Racemization mechanism of lithium tert-butylphenylphosphido-borane: A kinetic insight
Type de publication
Article de revue
Année de publication
2022
Revue
Chirality
Volume
34
Pagination
27–33
ISSN
1520-636X
Soumis le 12 janvier 2023