Aromaticity and sterics control whether a cationic olefin radical is resistant to disproportionation.

ABSTRACT: We elucidate why some electron rich-olefins such as tetrathiafulvalene (TTF) or paraquat (1,1'-dimethyl-4,4'-bipyridinylidene) form persistent radical cations, whereas others such as the dimer of N,N'-dimethyl benzimidazolin-2-ylidene (benzNHC) do not. Specifically, three heterodimers derived from cyclic (alkyl) (amino) carbenes (CAAC) with N,N'-dimethyl imidazolin-2-ylidene (NHC), N,N'-dimethyl imidazolidin-2-ylidene (saNHC) and N-methyl benzothiazolin-2-ylidene (btNHC) are reported. Whereas the olefin radical cations with the NHC and btNHC are isolable, the NHC compound with a saturated backbone (saNHC) disproportionates instead to the biscation and olefin. Furthermore, the electrochemical properties of the electron-rich olefins derived fr

SUBMITTER: Messelberger J 

PROVIDER: S-EPMC8562513 | biostudies-literature | 2020 Apr

REPOSITORIES: biostudies-literature