Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 140, Issue 46, Pages 15641-15645Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b10461
Keywords
-
Categories
Funding
- National Institutes of Health [GM056207]
- Center for Molecular Electrocatalysis, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences
- NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES [R37GM056207] Funding Source: NIH RePORTER
Ask authors/readers for more resources
Developing new strategies to activate and cleave C-H bonds is important for a broad range of applications. Recently a new approach for C-H bond activation using multi-site concerted proton-coupled electron transfer (PCET) involving intermolecular electron transfer to an oxidant coupled to intramolecular proton transfer was reported. For a series of oxidants reacting with 2-(9H-fluoren-9-yl)benzoate, experimental studies revealed an atypical Bronsted a, defined as the slope of the logarithm of the PCET rate constant versus the logarithm of the equilibrium constant or the scaled driving force. Herein this reaction is modeled with a vibronically nonadiabatic PCET theory. Hydrogen tunneling, thermal sampling of the proton donor-acceptor mode, solute and solvent reorganization, and contributions from excited vibronic states are found to play important roles. The calculations qualitatively reproduce the experimental observation of a Bronsted a significantly less than 0.5 and explain this shallow slope in terms of exoergic processes between pairs of electron proton vibronic states. These fundamental mechanistic insights may guide the design of more effective strategies for C-H bond activation and cleavage.
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