The Dewar Isomer of 1,2-Dihydro-1,2-azaborinines: Isolation, Fragmentation, and Energy Storage
Klara Edel
Institut für Organische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany
Search for more papers by this authorXinyu Yang
Department of Chemistry, Boston College, Chestnut Hill, MA, 02467-3860 USA
Search for more papers by this authorJacob S. A. Ishibashi
Department of Chemistry, Boston College, Chestnut Hill, MA, 02467-3860 USA
Search for more papers by this authorAshley N. Lamm
Department of Chemistry and Biochemistry, University of Oregon, Eugene, OR, 97403-1253 USA
Search for more papers by this authorCäcilia Maichle-Mössmer
Institut für Anorganische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany
Search for more papers by this authorZachary X. Giustra
Department of Chemistry, Boston College, Chestnut Hill, MA, 02467-3860 USA
Search for more papers by this authorCorresponding Author
Shih-Yuan Liu
Department of Chemistry, Boston College, Chestnut Hill, MA, 02467-3860 USA
Department of Chemistry and Biochemistry, University of Oregon, Eugene, OR, 97403-1253 USA
Search for more papers by this authorCorresponding Author
Holger F. Bettinger
Institut für Organische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany
Search for more papers by this authorKlara Edel
Institut für Organische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany
Search for more papers by this authorXinyu Yang
Department of Chemistry, Boston College, Chestnut Hill, MA, 02467-3860 USA
Search for more papers by this authorJacob S. A. Ishibashi
Department of Chemistry, Boston College, Chestnut Hill, MA, 02467-3860 USA
Search for more papers by this authorAshley N. Lamm
Department of Chemistry and Biochemistry, University of Oregon, Eugene, OR, 97403-1253 USA
Search for more papers by this authorCäcilia Maichle-Mössmer
Institut für Anorganische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany
Search for more papers by this authorZachary X. Giustra
Department of Chemistry, Boston College, Chestnut Hill, MA, 02467-3860 USA
Search for more papers by this authorCorresponding Author
Shih-Yuan Liu
Department of Chemistry, Boston College, Chestnut Hill, MA, 02467-3860 USA
Department of Chemistry and Biochemistry, University of Oregon, Eugene, OR, 97403-1253 USA
Search for more papers by this authorCorresponding Author
Holger F. Bettinger
Institut für Organische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany
Search for more papers by this authorAbstract
The photochemistry of 1,2-dihydro-1,2-azaborinine derivatives was studied under matrix isolation conditions and in solution. Photoisomerization occurs exclusively to the Dewar valence isomers upon irradiation with UV light (>280 nm) with high quantum yield (46 %). Further photolysis with UV light (254 nm) results in the formation of cyclobutadiene and an iminoborane derivative. The thermal electrocyclic ring-opening reaction of the Dewar valence isomer back to the 1,2-dihydro-1-tert-butyldimethylsilyl-2-mesityl-1,2-azaborinine has an activation barrier of (27.0±1.2) kcal mol−1. In the presence of the Wilkinson catalyst, the ring opening occurs rapidly and exothermically (ΔH=(−48±1) kcal mol−1) at room temperature.
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