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Azulenylcarbenes: Rearrangements on the C 11 H 8 Potential Energy Surface
Author(s) -
Henkel Stefan,
Pollok Corina H.,
Schleif Tim,
Sander Wolfram
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201601390
Subject(s) - singlet state , potential energy surface , chemistry , photodissociation , ground state , spectroscopy , photochemistry , carbene , electron paramagnetic resonance , computational chemistry , atomic physics , excited state , physics , molecule , catalysis , organic chemistry , nuclear magnetic resonance , quantum mechanics
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 C 11 H 8 isomers, such as other carbenes and strained allenes.