| Autor: |
Ramírez-Solís, Alejandro, Boekell, Nicholas G., León-Pimentel, César Iván, Saint-Martin, Humberto, Bartulovich, Caroline O., Flowers, Robert A. |
| Zdroj: |
The Journal of Organic Chemistry; 20210101, Issue: Preprints |
| Abstrakt: |
Coordination-induced desolvation or ligand displacement by cosolvents and additives is a key feature responsible for the reactivity of Sm(II)-based reagent systems. High-affinity proton donor cosolvents such as water and glycols also demonstrate coordination-induced bond weakening of the O–H bond, facilitating reduction of a broad range of substrates. In the present work, the coordination of ammonia to SmI2was examined using Born–Oppenheimer molecular dynamics simulations and mechanistic studies, and the SmI2-ammonia system is compared to the SmI2-water system. The coordination number and reactivity of the SmI2-ammonia solvent system were found to be similar to those of SmI2-water but exhibited an order of magnitude greater rate of arene reduction by SmI2-ammonia than by SmI2-water at the same concentrations of cosolvent. In addition, upon coordination of ammonia to SmI2, the Sm(II)-ammonia solvate demonstrates one of the largest degrees of N–H bond weakening reported in the literature compared to known low-valent transition metal ammonia complexes. |
| Databáze: |
Supplemental Index |
| Externí odkaz: |
|
