We present here a combined experimental and computational investigation into the photorearrangement of N-cyclopropylimines to yield pyrrolines. We show that the photochemistry, regiochemistry, and stereochemistry of the reaction can be understood in terms of a mechanism involving barrierless evolution in three different (S2, S1, S0) singlet states and sequential decay through two different (S2/S1, and S 1/S0) conical intersection funnels. We provide evidence that the reaction mechanism involves the generation of a nonequilibrated (i.e., transient) excited state diradical, whose decay can lead not only to pyrrolines but also to cyclopropylimine isomers. It is concluded that the reaction outcome depends on the details of the structure of such transient diradical and on the nature of the dynamics of its decay through the S1/S0 conical intersection.
Sampedro, D., Soldevilla, A., Rodrguez, M.A., Campos, P.J., Olivucci, M. (2005). The Mechanism of the N-Cyclopropylimine-1-Pyrroline Photorearrangement. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 127(1), 441-448 [10.1021/ja0467566].
The Mechanism of the N-Cyclopropylimine-1-Pyrroline Photorearrangement
Olivucci, Massimo
2005-01-01
Abstract
We present here a combined experimental and computational investigation into the photorearrangement of N-cyclopropylimines to yield pyrrolines. We show that the photochemistry, regiochemistry, and stereochemistry of the reaction can be understood in terms of a mechanism involving barrierless evolution in three different (S2, S1, S0) singlet states and sequential decay through two different (S2/S1, and S 1/S0) conical intersection funnels. We provide evidence that the reaction mechanism involves the generation of a nonequilibrated (i.e., transient) excited state diradical, whose decay can lead not only to pyrrolines but also to cyclopropylimine isomers. It is concluded that the reaction outcome depends on the details of the structure of such transient diradical and on the nature of the dynamics of its decay through the S1/S0 conical intersection.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
https://hdl.handle.net/11365/8115
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