UCSD-CNRS Joint Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA 92093-0343 (USA) http://bertrandgroup.ucsd.edu.
Karlsruhe Institute of Technology (KIT), Institute of Inorganic Chemistry, Engesserstrasse 15, 76131 Karlsruhe (Germany).
Chemistry. 2015 Jun 1;21(23):8441-6. doi: 10.1002/chem.201500740. Epub 2015 Apr 29.
A stable cyclic (alkyl)(amino)carbene (CAAC) 1 inserts into the para-CF bond of pentafluoropyridine, and after fluoride abstraction, the iminium-pyridyl adduct 3 was isolated. A cyclic voltammetry study shows a reversible three-state redox system involving 3 , 3 , and 3 . The CAAC-pyridyl radical 3 , obtained by reduction of 3 with magnesium, has been spectroscopically and crystallographically characterized. In contrast to the lack of π communication between the CAAC and the pyridine units in cation 3 , the unpaired electron of 3 is delocalized over an extended π system involving both heterocycles.
