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NHC‐CAAC Heterodimers with Three Stable Oxidation States
Author(s) -
Munz Dominik,
Chu Jiaxiang,
Melaimi Mohand,
Bertrand Guy
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201607537
Subject(s) - carbene , protonation , iminium , cyclic voltammetry , deprotonation , chemistry , cationic polymerization , salt (chemistry) , acetonitrile , radical , photochemistry , polymer chemistry , electrochemistry , organic chemistry , ion , catalysis , electrode
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).