Electroanalytical and Computational Investigation of Oxoammonium-Mediated Hydride Transfer.
- 1Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York14853, United States.
- 2Department of Chemistry, Stanford University, Stanford, California94305, United States.
Abstract
Oxoammonium-mediated hydride transfer is an important yet relatively underexplored elementary step in C-H functionalization. In this work, we employed cyclic voltammetry (CV) to measure the rates of hydride transfer between electrochemically generated oxoammonium catalysts and 42 substrates including ethers, carbamates, amides, and sulfonamides. Through quantum mechanical (QM) calculations, we uncovered a new transition-state model for hydride transfer in which the N atom of the catalyst resides near a heteroatom (X = N or O) of the substrate to allow alignment of the oxoammonium's O═N+ motif and the substrate's forming C═X+ bond. Energy decomposition analysis was subsequently performed to elucidate the key factors that govern the kinetics of oxoammonium-mediated hydride transfer. Beyond conventional electronic and steric considerations, we identified substrate distortion, secondary orbital interactions, and noncovalent interactions as critical factors that influence hydride transfer reactivity. We anticipate that these kinetic data along with the mechanistic insights they provide will inform future catalyst development and synthetic applications to broaden the scope of oxoammonium catalysis.
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BibTeX
@article{kandahari2026electroanalytical,
title = {{Electroanalytical and Computational Investigation of Oxoammonium-Mediated Hydride Transfer.}},
author = {Elya Kandahari and Natalie A Cox and Yi Wang and Song Lin},
journal = {Journal of the American Chemical Society},
year = {2026},
month = oct,
doi = {10.1021/jacs.6c10904},
url = {https://europepmc.org/article/MED/42912349},
note = {CC BY-NC-ND},
}
RIS
TY - JOUR
TI - Electroanalytical and Computational Investigation of Oxoammonium-Mediated Hydride Transfer.
AU - Elya Kandahari
AU - Natalie A Cox
AU - Yi Wang
AU - Song Lin
PY - 2026
DA - 2026/10/01
JO - Journal of the American Chemical Society
DO - 10.1021/jacs.6c10904
UR - https://europepmc.org/article/MED/42912349
AB - Oxoammonium-mediated hydride transfer is an important yet relatively underexplored elementary step in C-H functionalization. In this work, we employed cyclic voltammetry (CV) to measure the rates of hydride transfer between electrochemically generated oxoammonium catalysts and 42 substrates including ethers, carbamates, amides, and sulfonamides. Through quantum mechanical (QM) calculations, we uncovered a new transition-state model for hydride transfer in which the N atom of the catalyst resides near a heteroatom (X = N or O) of the substrate to allow alignment of the oxoammonium's O═N+ motif and the substrate's forming C═X+ bond. Energy decomposition analysis was subsequently performed to elucidate the key factors that govern the kinetics of oxoammonium-mediated hydride transfer. Beyond conventional electronic and steric considerations, we identified substrate distortion, secondary orbital interactions, and noncovalent interactions as critical factors that influence hydride transfer reactivity. We anticipate that these kinetic data along with the mechanistic insights they provide will inform future catalyst development and synthetic applications to broaden the scope of oxoammonium catalysis.
SN - 0002-7863
SN - 1520-5126
ER -