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Page 6 of 8
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ceed through PCET. The complexity of the reduction
resulting from PCET shows that care should be em-
ployed when interpreting deuterium isotope effects or
mechanisms deduced from empirical models based on
knowledge of ground state reductants and reaction
products alone. Although the studies presented herein
reveal the complexity of arene reduction by Sm(II)-water,
these results may have an important impact for the re-
duction of other functional groups. This is especially
important for carbonyls and related functional groups
that are likely to compete with water for coordination to
Sm(II). We are currently examining these systems and
the results of these studies will be reported in due
course.
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ASSOCIATED CONTENT
Experimental procedures, kinetic and spectral data. This
material is available free of charge via the Internet at
AUTHOR INFORMATION
Corresponding Author
*rof2@lehigh.edu
Author Contributions
The manuscript was written through contributions of both
authors who have given approval to the final version of the
manuscript.
Funding Sources
RAF is grateful to the National Science Foundation (CHE
1266333) for support of this work.
ACKNOWLEDGMENT
(10) Enemaerke, R.J.; Daasbjerg, K.; Skrydstrup, T. Chem.
Comm. 1999, 343-344.
We thank Drs. James Devery, Lawrence Courtney, Niki
Patel, and Rebecca Miller for insightful discussions. We
also thank reviewers for constructive evaluation and feed-
back. RAF thanks Professor R. Stan Brown for insightful
discussions on rare earth-water complexes.
(11) Miller, R.S.; Sealy, J.M.; Fuchs, J.R.; Shabangi, M.;
Flowers, R.A., II J. Am. Chem. Soc. 2000, 122, 7718-7722.
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2014, 79, 2522-2537.
(15) Vanýsek, P.; CRC Handbook of Chemistry and Physics.
Lide, D. R.; 85th ed.; CRC Press: Boca Raton, FL, 2004-2005;
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ABBREVIATIONS
ET, electron transfer; PT, proton transfer; PCET, proton
coupled electron transfer; THF, tetrahydrofuran.
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