Electrochemical Deoxygenation of a TiIV-Oxo Complex to Enable Catalytic Reductive Oxygen-Atom Transfer from Organic Molecules.
- 1Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin53706, United States.
Abstract
Well-defined (TTP)TiII (TTP = 5,10,15,20-tetratolylporphyrin) complexes have been shown to promote stoichiometric deoxygenation of organic molecules, such as sulfoxides and epoxides, forming a stable (TTP)TiIV=O product. Here, we explore strategies to promote catalytic deoxygenation reactivity by regenerating (TTP)TiII through chemical or electrochemical reduction. A survey of Lewis acids revealed the effectiveness of B(OPh)3 in promoting activation and loss of the Ti-oxo group, enabling TiII-mediated reductive oxygen-atom transfer (OAT) of diphenyl sulfoxide. Cyclic voltammetry, coulometry, EPR spectroscopy, and X-ray crystallography have been used to probe and characterize TiIII and TiII species from the electroreductive deoxygenation of the TiIV=O complex. The data implicate a Lewis-acid-coupled electron-transfer deoxygenation pathway for TiIV=O turnover. These fundamental studies are complemented by electrochemical reactions demonstrating catalytic reductive oxygen-atom transfer from sulfoxides, pyridine N-oxides, and epoxides.
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BibTeX
@article{deng2026electrochemical,
title = {{Electrochemical Deoxygenation of a TiIV-Oxo Complex to Enable Catalytic Reductive Oxygen-Atom Transfer from Organic Molecules.}},
author = {Ruohan Deng and Tianxiao Jiang and Haoran Chen and Ilia A Guzei and Leah C Garman and Xianyuan Zhao and Yang Yang and Shannon S Stahl},
journal = {Journal of the American Chemical Society},
year = {2026},
month = sep,
doi = {10.1021/jacs.6c11967},
url = {https://europepmc.org/article/MED/42915524},
note = {CC BY},
}
RIS
TY - JOUR
TI - Electrochemical Deoxygenation of a TiIV-Oxo Complex to Enable Catalytic Reductive Oxygen-Atom Transfer from Organic Molecules.
AU - Ruohan Deng
AU - Tianxiao Jiang
AU - Haoran Chen
AU - Ilia A Guzei
AU - Leah C Garman
AU - Xianyuan Zhao
AU - Yang Yang
AU - Shannon S Stahl
PY - 2026
DA - 2026/09/01
JO - Journal of the American Chemical Society
DO - 10.1021/jacs.6c11967
UR - https://europepmc.org/article/MED/42915524
AB - Well-defined (TTP)TiII (TTP = 5,10,15,20-tetratolylporphyrin) complexes have been shown to promote stoichiometric deoxygenation of organic molecules, such as sulfoxides and epoxides, forming a stable (TTP)TiIV=O product. Here, we explore strategies to promote catalytic deoxygenation reactivity by regenerating (TTP)TiII through chemical or electrochemical reduction. A survey of Lewis acids revealed the effectiveness of B(OPh)3 in promoting activation and loss of the Ti-oxo group, enabling TiII-mediated reductive oxygen-atom transfer (OAT) of diphenyl sulfoxide. Cyclic voltammetry, coulometry, EPR spectroscopy, and X-ray crystallography have been used to probe and characterize TiIII and TiII species from the electroreductive deoxygenation of the TiIV=O complex. The data implicate a Lewis-acid-coupled electron-transfer deoxygenation pathway for TiIV=O turnover. These fundamental studies are complemented by electrochemical reactions demonstrating catalytic reductive oxygen-atom transfer from sulfoxides, pyridine N-oxides, and epoxides.
SN - 0002-7863
SN - 1520-5126
ER -