Crystalline Cyclic (Alkyl)(amino)carbene‐tetrafluoropyridyl Radical |
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| Authors: | Steffen Styra Dr. Mohand Melaimi Dr. Curtis E. Moore Prof. Arnold. L. Rheingold Timo Augenstein Prof. Dr. Frank Breher Prof. Guy Bertrand |
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| Affiliation: | 1. 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;2. Karlsruhe Institute of Technology (KIT), Institute of Inorganic Chemistry, Engesserstrasse 15, 76131 Karlsruhe (Germany);3. UCSD Crystallography Facility, Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA 92093‐0343 (USA) |
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| Abstract: | 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. |
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| Keywords: | carbenes cyclic voltammetry radicals redox chemistry |
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