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Article

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

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Yuxia Liu, Thomas C. Stringfellow, David Ballweg, Ilia A. Guzei, and Robert West*

Contribution from the Organosilicon Research Center, Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706

J. Am. Chem. Soc., 2002, 124 (1), pp 49–57

DOI: 10.1021/ja011821m

Publication Date (Web): December 6, 2001

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

Abstract

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.

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Published In Issue January 09, 2002
Received July 26, 2001

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Article

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

Abstract

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