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Competition Between Concerted and Stepwise Dynamics in the Triplet Di‐π‐Methane Rearrangement
Author(s) -
JiménezOsés Gonzalo,
Liu Peng,
Matute Ricardo A.,
Houk Kendall N.
Publication year - 2014
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.201310237
Subject(s) - competition (biology) , methane , dynamics (music) , chemistry , physics , biology , ecology , organic chemistry , acoustics
The molecular dynamics of the triplet‐state Zimmerman di‐π‐methane rearrangement of dibenzobarrelene were computed with B3LYP and M06‐2X density functionals. All productive quasiclassical trajectories involve sequential formation and cleavage of CC bonds and an intermediate with lifetimes ranging from 13 to 1160 fs. Both dynamically concerted and stepwise trajectories are found. The average lifetime of this intermediate is significantly shorter than predicted by either transition‐state theory or the Rice–Ramsperger–Kassel–Marcus model, thus indicating the non‐statistical nature of the reaction mechanism.