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 (29)Si 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 Me(3)SiCl 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 (29)Si 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.
Liu
Yuxia
Y
Organosilicon Research Center, Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, USA.
Stringfellow
Thomas C
TC
Ballweg
David
D
Guzei
Ilia A
IA
West
Robert
R
D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D005609:Free Radicals / Q000737:chemistry; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D017646:Organosilicon Compounds / Q000737:chemistry*; D013816:Thermodynamics
C447721:1-silafluorenyl dianion; D005609:Free Radicals; D017646:Organosilicon Compounds