Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 24, Issue 35, Pages 20721-20727Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d2cp02733j
Keywords
-
Funding
- American Chemical Society Petroleum Research Fund (ACS PRF) [60481-ND6]
Ask authors/readers for more resources
Efficient activation and functionalization of the C-H bond under mild conditions are of great interest in chemical synthesis. This study investigates a previously proposed method and proposes a more favorable reaction pathway for C-H bond activation.
Efficient activation and functionalization of the C-H bond under mild conditions are of a great interest in chemical synthesis. We investigate the previously proposed spin-accelerated activation of the C(sp(2))-H bond by a Fe(ii)-based catalyst to clarify the role of the intermediate triplet state in the reaction mechanism. High-level electronic structure calculations on a small model of a catalytic system utilizing the coupled cluster with the single, double, and perturbative triple excitations [CCSD(T)] are used to select the density functional for the full-size model. Our analysis indicates that the previously proposed two-state quintet-singlet reaction pathway is unlikely to be efficient due to a very weak spin-orbit coupling between these two spin states. We propose a more favorable multi-state quintet-triplet-singlet reaction pathway and discuss the importance of the intermediate triplet state. This triplet state facilitates a spin-accelerated reaction mechanism by strongly coupling to both quintet and singlet states. Our calculations show that the C-H bond activation through the proposed quintet-triplet-singlet reaction pathway is more thermodynamically favorable than the single-state quintet and two-state singlet-quintet mechanisms.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available