TY - JOUR
T1 - Intramolecular Hydrogen Atom Transfer in Aminyl Radical at Room Temperature with Large Kinetic Isotope Effect
AU - Wang, Ying
AU - Olankitwanit, Arnon
AU - Rajca, Suchada
AU - Rajca, Andrzej
N1 - Funding Information:
We thank the NSF (CHE-1362454 and CHE-1665256) and NIH (R01 EB-019950-01A1) for support of this research.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/5/31
Y1 - 2017/5/31
N2 - We report a large kinetic isotope effect at 298 K, kH/kD ≈ 150, associated with an intramolecular 1,5-hydrogen atom transfer (1,5-HAT) in the decay of a PEGylated carbazyl (aminyl) radical in solution. The experimental observations surprisingly combine the hallmarks of tunneling, including large KIEs and unusual activation parameters, with linear Arrhenius and Eyring plots over an exceptionally wide temperature range of 116 K.
AB - We report a large kinetic isotope effect at 298 K, kH/kD ≈ 150, associated with an intramolecular 1,5-hydrogen atom transfer (1,5-HAT) in the decay of a PEGylated carbazyl (aminyl) radical in solution. The experimental observations surprisingly combine the hallmarks of tunneling, including large KIEs and unusual activation parameters, with linear Arrhenius and Eyring plots over an exceptionally wide temperature range of 116 K.
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U2 - 10.1021/jacs.7b02692
DO - 10.1021/jacs.7b02692
M3 - Article
C2 - 28514849
AN - SCOPUS:85019977416
SN - 0002-7863
VL - 139
SP - 7144
EP - 7147
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 21
ER -