Azulenylcarbenes: Rearrangements on the C11H8 Potential Energy Surface

作者:Henkel Stefan; Pollok Corina H; Schleif Tim; Sander Wolfram*
来源:Chemistry - A European Journal, 2016, 22(35): 12479-12486.
DOI:10.1002/chem.201601390

摘要

Four isomeric azulenylcarbenes were synthesized in argon matrices by photolysis of the corresponding diazo precursors, and the photochemistry of these carbenes was studied. The carbenes and their rearranged products were characterized by IR, UV/Vis, and EPR spectroscopy, and the experimental data were compared to results from DFT calculations. While 2-, 5- and 6-azulenylcarbene show triplet ground states, 1-azulenylcarbene exhibits a singlet ground state, in accord with theoretical predictions. The rearrangements of the azulenylcarbenes give access to a number of unusual C11H8 isomers, such as other carbenes and strained allenes.

  • 出版日期2016-8-22