Access to 1,3-dineopentyl-benzimidazol-2-ylidene ( 1) by deprotonation of various benzimidazolium salts was studied. [Ag( 1)Cl] was prepared from the corresponding benzimidazolium chloride. X-ray crystal structure analyses of benzo-, naphtho- and quinoxalino-anellated imidazolium salts displayed neither significant changes nor systematic trends of bond lengths and angles within the five-membered ring. Consistently downfield shifts of the 13C 1H(2) nuclei reflect the influence of electron-withdrawing anellation.