TY - JOUR
T1 - External Electric Fields Interrupt the Concerted Cope Rearrangement of Semibullvalene
AU - Laconsay, Croix J.
AU - Mallick, Dibyendu
AU - Shaik, Sason
N1 - Publisher Copyright:
© 2020 American Chemical Society.
PY - 2021/1/1
Y1 - 2021/1/1
N2 - The topic of this paper is whether the mechanism of the degenerate Cope rearrangement of semibullvalene can be affected by the presence of electrostatic fields. Herein, we report that the shape of the energy surface, as demonstrated by an "interrupted"(stepwise) mechanism, is altered in the presence of a copper cation, Cu+. Natural bond-orbital and block-localized wave-function energy decomposition analyses suggest that orbital and electrostatic interactions play a major role in altering the shape of the energy surface. Applying additional external electric fields (EEFs) induces a significant change to the energy surface with Cu+ present but negligible effects in the absence of Cu+. These findings are consistent with recent studies that demonstrate that EEFs more readily stabilize/destabilize systems with larger, more polarizable, dipole moments.
AB - The topic of this paper is whether the mechanism of the degenerate Cope rearrangement of semibullvalene can be affected by the presence of electrostatic fields. Herein, we report that the shape of the energy surface, as demonstrated by an "interrupted"(stepwise) mechanism, is altered in the presence of a copper cation, Cu+. Natural bond-orbital and block-localized wave-function energy decomposition analyses suggest that orbital and electrostatic interactions play a major role in altering the shape of the energy surface. Applying additional external electric fields (EEFs) induces a significant change to the energy surface with Cu+ present but negligible effects in the absence of Cu+. These findings are consistent with recent studies that demonstrate that EEFs more readily stabilize/destabilize systems with larger, more polarizable, dipole moments.
UR - http://www.scopus.com/inward/record.url?scp=85097886562&partnerID=8YFLogxK
U2 - 10.1021/acs.joc.0c02322
DO - 10.1021/acs.joc.0c02322
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AN - SCOPUS:85097886562
SN - 0022-3263
VL - 86
SP - 731
EP - 738
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 1
ER -