TY - JOUR
T1 - Electron flow in reaction mechanisms - Revealed from first principles
AU - Knizia, Gerald
AU - Klein, Johannes E.M.N.
N1 - Publisher Copyright:
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2015/4/27
Y1 - 2015/4/27
N2 - The "curly arrow" of Robinson and Ingold is the primary tool for describing and rationalizing reaction mechanisms. Despite this approach's ubiquity and stellar success, its physical basis has never been clarified and a direct connection to quantum chemistry has never been found. Here we report that the bond rearrangements expressed by curly arrows can be directly observed in ab initio computations, as transformations of intrinsic bond orbitals (IBOs) along the reaction coordinate. Our results clarify that curly arrows are rooted in physical reality - a notion which has been challenged before - and show how quantum chemistry can directly establish reaction mechanisms in intuitive terms and unprecedented detail.
AB - The "curly arrow" of Robinson and Ingold is the primary tool for describing and rationalizing reaction mechanisms. Despite this approach's ubiquity and stellar success, its physical basis has never been clarified and a direct connection to quantum chemistry has never been found. Here we report that the bond rearrangements expressed by curly arrows can be directly observed in ab initio computations, as transformations of intrinsic bond orbitals (IBOs) along the reaction coordinate. Our results clarify that curly arrows are rooted in physical reality - a notion which has been challenged before - and show how quantum chemistry can directly establish reaction mechanisms in intuitive terms and unprecedented detail.
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U2 - 10.1002/anie.201410637
DO - 10.1002/anie.201410637
M3 - Article
AN - SCOPUS:85027920707
VL - 54
SP - 5518
EP - 5522
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 18
ER -