[en] The synthesis of zwitterionic dithiocarboxylate adducts was achieved by deprotonating various aldiminium or 1,2,3-triazolium salts with a strong base, followed by the nucleophilic addition of the in situ-generated cyclic (alkyl)(amino) or mesoionic carbenes (CAACs or MICs) onto carbon disulfide. Nine novel compounds were isolated and fully characterized by 1H and 13C NMR, FTIR, and HRMS techniques. Moreover, the molecular structures of two CAAC·CS2 and two MIC·CS2 betaines were determined by X-ray diffraction analysis. The analytical data recorded for all these adducts were compared with those reported previously for related NHC·CS2 betaines derived from imidazolinium or (benz)imidazolium salts. Due to the absence of electronic communication between the CS2 unit and the orthogonal heterocycle, all the CAAC·CS2, MIC·CS2, and NHC·CS2 zwitterions displayed similar electronic properties and featured the same bite angle. Yet, their steric properties are liable to ample modifications by varying the exact nature of their cationic heterocycle and its substituents.
Disciplines :
Chemistry
Author, co-author :
Touj, Nedra ; Laboratory of Catalysis, MolSys Research Unit, Université de Liège, Institut de chimie organique (B6a), Allée du six août 13, 4000 Liège, Belgium
Mazars, François ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie organométallique et catalyse homogène
Zaragoza, Guillermo ; Unidad de Difracción de Rayos X, RIAIDT, Universidade de Santiago de Compostella, Edificio CACTUS, Campus Vida, 15782 Santiago de Compostela, Spain
Delaude, Lionel ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie organométallique et catalyse homogène
Language :
English
Title :
Aldiminium and 1,2,3-triazolium dithiocarboxylate zwitterions derived from cyclic (alkyl)(amino) and mesoionic carbenes.
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