title: NHC-CAAC Heterodimers with Three Stable Oxidation States.
abstract: The synthesis of N-heterocyclic carbene (NHC)-cyclic (alkyl)(amino) carbene (CAAC) heterodimers is presented. As the free carbenes do not react together in solution, the synthetic approach involves the addition of a free NHC to a cyclic iminium salt, which results in the formation of the protonated heterodimer. Subsequent deprotonation leads to the isolation of the corresponding mixed Wanzlick dimers. One- and two-electron oxidations of these triazaolefins result in the formation of stable cationic radicals and bis(cations), respectively, which have been isolated and fully characterized. Cyclic voltammetry, UV/Vis spectroscopy, spin density, and DFT calculations suggest that these heterodimers feature complementary electronic properties to tetrathiafulvalenes (TTFs).
authors.affiliation: Joint UCSD-CNRS Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA, 92093-0358, USA.
authors.forename: Dominik
authors.identifier: 0000-0003-3412-651X
authors.initials: D
authors.lastname: Munz
authors.affiliation: Joint UCSD-CNRS Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA, 92093-0358, USA.
authors.forename: Jiaxiang
authors.identifier: 0000-0002-2755-093X
authors.initials: J
authors.lastname: Chu
authors.affiliation: Joint UCSD-CNRS Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA, 92093-0358, USA.
authors.forename: Mohand
authors.identifier: 0000-0003-3553-1381
authors.initials: M
authors.lastname: Melaimi
authors.affiliation: Joint UCSD-CNRS Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA, 92093-0358, USA. guybertrand@ucsd.edu.
authors.forename: Guy
authors.identifier: 0000-0003-2623-2363
authors.initials: G
authors.lastname: Bertrand
keywords: CAAC; N-heterocyclic carbenes; electron-rich olefins; radical cations; tetrathiafulvalenes