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The Mechanism of Interaction of Triplet 3‐Methylcyclohex‐2‐en‐1‐one with Maleo‐ and fumarodinitrile: Evidence for Direct Formation of Triplet 1,4‐Biradicals in [2 + 2] Photocyclo‐ additions without the Intermediacy of Exciplexes
Author(s) -
Schuster David I.,
Heibel George E.,
Woning Jan
Publication year - 1991
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.199113451
Subject(s) - diradical , chemistry , conformational isomerism , alkene , photochemistry , cycloaddition , triplet state , mechanism (biology) , computational chemistry , singlet state , physics , molecule , organic chemistry , quantum mechanics , catalysis , excited state
Alkene–enone exciplexes can be excluded as intermediates in the [2 + 2] cycloaddition of fumarodinitrile and triplet 3‐methylcyclohex‐2‐en‐1‐one. Instead, the experimental results demonstrate that the triplet 1,4‐diradical intermediate 1 is favored, which rapidly forms an equilibrium mixture of rotamers about the newly formed single bond before reacting to form the corresponding cycloadducts.