| Autor: |
VanderWeide, Andrew I., Neugebauer, Hagen, Goel, Bhumika, Tresp, David S., Pena, Deuris, Grimme, Stefan, Hansen, Andreas, Prokopchuk, Demyan E. |
| Zdroj: |
Organometallics; December 2024, Vol. 43 Issue: 24 p3143-3152, 10p |
| Abstrakt: |
We show that amine-rich CpN3ligands coordinated to iron display chemically noninnocent behavior in the presence of exogenous hydride donors (CpN3= 1,4-dimethyl-5,7-diphenyl-6-(pyrrolidin-1-yl)-2,3,4,6-tetrahydro-1H-cyclopenta[b]pyrazin-6-yl). The reaction of piano-stool iron complex [(CpN3)Fe(CO)3]+with three different hydride reagents furnishes three different iron complexes, two of which result in net H–transfer to the CpN3ligand. Exposure of [(CpN3)Fe(CO)3]+to NaHBEt3results in endo hydride addition to the CpN3ligand, reaction with NaBH4yields an exo-CpN3H product, and an iron hydride complex forms in the presence of [nBu4N][HCOO]. While state-of-the-art DFT computations indicate that NaBH4addition to [(CpN3)Fe(CO)3]+happens via direct H–transfer to the CpN3ligand, reactions with HBEt3–or HCOO–initially generate a key iron formyl intermediate which has been experimentally observed. Herein, we present a blend of experimental and computational data to unravel some elementary steps that lead to the formation of these chemically distinct hydride addition products. |
| Databáze: |
Supplemental Index |
| Externí odkaz: |
|
