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Nuclear Resonance Vibrational Spectroscopy on the Fe IV O S =2 Non‐Heme Site in TMG 3 tren: Experimentally Calibrated Insights into Reactivity
Author(s) -
Wong Shaun D.,
Bell Caleb B.,
Liu Lei V.,
Kwak Yeonju,
England Jason,
Alp E. Ercan,
Zhao Jiyong,
Que Lawrence,
Solomon Edward I.
Publication year - 2011
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201007692
Subject(s) - steric effects , reactivity (psychology) , resonance (particle physics) , chemistry , nuclear magnetic resonance spectroscopy , spectroscopy , nuclear magnetic resonance , atomic physics , physics , stereochemistry , quantum mechanics , medicine , alternative medicine , pathology
Dissecting the barrier : The nuclear resonance vibrational spectrum of the S =2 [(TMG 3 tren)Fe IV O] complex revealed features indicative of an axial “steric wall” that contributes to the overall reaction barrier. DFT calculations show that both S =2 (axial attack) and S =1 (equatorial attack) surfaces possess steric contributions to their barriers, and estimates of these steric effects result in comparable intrinsic barriers for both spin surfaces (see picture).