Structure and Chemistry of 1-Silafluorenyl Dianion, Its Derivatives, and an Organosilicon Diradical Dianion

1-Silafluorene dianion was synthesized by potassium reduction of 1,1-dichloro-1-silafluorene in
refluxing THF. The X-ray structure of 1,1-dipotassio-1-silafluorene (3b) shows C−C bond length equalization
in the five-membered silole ring and C−C bond length alternation in the six-membered benzene rings,
indicating aromatic delocalization of electrons in the silole ring. The downfield 29Si chemical shift at 29.0
ppm and theoretical calculations also support electron delocalization in the silole ring of 3b. Dianion salt
3b underwent nucleophilic reactions with Me3SiCl and EtBr to form the corresponding disubstituted products.
Benzaldehyde underwent reductive coupling in the presence of 3b. Slow oxidation of 3b yielded 1,1‘-dipotassio-1,1‘-bis(silafluorene) (16). The X-ray structure and 29Si chemical shift (−38.0 ppm) of 16 indicate
localized negative charges at the silicon atoms and no aromatic character. Heating a DME/hexane solution
of 3b in the presence of 18-crown-6 led to a novel diradical dianion salt.