High-Affinity Proton Donors Promote Proton-Coupled Electron Transfer by Samarium Diiodide

The relationship between proton‐donor affinity for SmII ions and the reduction of two substrates (anthracene and benzyl chloride) was examined. A combination of spectroscopic, thermochemical, and kinetic studies show that only those proton donors that coordinate or chelate strongly to SmII promote a...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2016-05, Vol.55 (20), p.6033-6036
Main Authors: Chciuk, Tesia V., Anderson Jr, William R., Flowers II, Robert A.
Format: Article
Language:English
Subjects:
Affinity
Anthracene
Chelates
Electron transfer
hydrogen-atom transfer
Kinetics
proton donors
proton-coupled electron transfer
Protons
Reagents
Reduction
Samarium
samarium diiodide
Substrates
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Summary:The relationship between proton‐donor affinity for SmII ions and the reduction of two substrates (anthracene and benzyl chloride) was examined. A combination of spectroscopic, thermochemical, and kinetic studies show that only those proton donors that coordinate or chelate strongly to SmII promote anthracene reduction through a PCET process. These studies demonstrate that the combination of SmII ions and water does not provide a unique reagent system for formal hydrogen atom transfer to substrates. Very Sm‐art! A combination of thermochemical, spectroscopic, and kinetic studies demonstrate that only proton donors with a high affinity for SmI2 promote reduction of anthracene through a PCET process. In fact, any high‐affinity ligand containing a strong X–H bond that is weakened upon coordination to a metal could be effective for reduction.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201601474