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Journal Name
COMMUNICATION
Conclusions
DOI: 10.1039/C9SC02609F
The results outlined herein demonstrate the
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electrochemical generation of high valent iron species via
III
proton-coupled oxidation of a TAML-ligated Fe –OH
2
complex,
and the application of this reaction to preparative
electrochemical oxidation of organic molecules. Voltammetry
2
8.
3
4
a) Che, C.-M.; Lo, V. K.-L.; Zhou, C.-Y.; Huang, J.-S. Chem. Soc. Rev.
IV
V
analysis reveals the sequential formation of Fe and Fe species
at increasing potentials (800 and 1250 mV, respectively).
2
2
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III
–
Electrolysis of [(TAML)Fe (OH
2
)] at the higher potential results
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IV
in accumulation of the oxo-bridged, dimeric (TAML)Fe species
V
3
in solution, attributed to the generation of Fe at the
III
electrode followed by comproportionation with Fe in solution.
Sustained electrolysis at this potential provides the basis for
selective electrochemical organic oxidation reactions, including
oxygenation of benzylic C–H bonds and dehydrogenation of
alcohols.
2
2
007, 315, 835–838. b) Comba, P.; Wunderlich, S. Chem. Eur. J.
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These results establish an important foundation for future
studies, such as those focused on the development of more
robust metal complexes. The self-promoted decomposition of
the high-valent intermediates generated under these reaction
conditions limits the Faradaic efficiency and the catalyst lifetime
during electrolysis. Furthermore, complexes that exhibit
stability under acidic conditions could support broader
functional group compatibility by taking advantage of the ability
to protect amines and other basic functional groups via
3
2
protonation with a Brønsted acid.
1
5833–15842.
Conflict of interest
There are no conflicts to declare.
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6
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319–5324.
Acknowledgements
This project was initiated with financial support from an NSF CCI
grant (CHE-1305124) and completed with support from the DOE
For electrochemical generation of high valent iron-oxo
complexes (i.e., non-catalytic examples), see: a) Lee, W. A.;
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DE-FG02-05ER15690). JEN acknowledges the NSF for
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predoctoral fellowship (DGE-1747503). The spectrometers
were supported by NSF grant CHE-1048642 and by a generous
gift from Paul J. and Margaret M. Bender, and the mass
spectrometer was supported by NIH grant NIH 1S10 OD020022-
7
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Notes and references
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