We report the synthesis and structural study of 2-substituted 1,3-bis(dimethylamino)pentalenes. The two-electrons donating substituents shift the formally anti-aromatic pattern toward more suited polarized structures. A subtle steric trade off can result either in planar cyclopentadienyl vinamidiniums, or in distorted structures featuring a pyramidalized ylidic carbon adjacent to a stabilized p-conjugated iminium (polymethine). This latter pattern mimics a postulated activated distorted geometry for key Breslow intermediates in the active site of thiamine-dependent enzymes. It highlights how the energetic drive to avoid anti-aromaticity can be used to access models for unconventional distorted conformations of organic molecules.