Molecules 2013, 18(9), 10568-10579; doi:10.3390/molecules180910568
Article

Synthesis and NMR-Study of 1-Trimethylsilyl Substituted Silole Anion [Ph4C4Si(SiMe3)]•[Li]+ and 3-Silolenide 2,5-carbodianions {[Ph4C4Si(n-Bu)2]2•2[Li]+, [Ph4C4Si(t-Bu)2]2•2[Li]+} via Silole Dianion [Ph4C4Si]2•2[Li]+

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Received: 24 July 2013; in revised form: 21 August 2013 / Accepted: 22 August 2013 / Published: 30 August 2013
(This article belongs to the Section Organic Synthesis)
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Abstract: 1-Trimethylsilyl, 1-R (R = Me, Et, i-Bu)-2,3,4,5-tetraphenyl-1-silacyclopentadiene [Ph4C4Si(SiMe3)R] are synthesized from the reaction of 1-trimethylsilyl,1-lithio-2,3,4,5-tetraphenyl-1-silacyclopentadienide anion [Ph4C4SiMe3]•[Li]+ (3) with methyl iodide, ethyl iodide, and i-butyl bromide. The versatile intermediate 3 is prepared by hemisilylation of the silole dianion [Ph4C4Si]−2•2[Li]+ (2) with trimethylsilyl chloride and characterized by 1H-, 13C-, and 29Si-NMR spectroscopy. 1,1-bis(R)-2,3,4,5-tetraphenyl-1-silacyclopentadiene [Ph4C4SiR2] {R = n-Bu (7); t-Bu (8)} are synthesized from the reaction of 2 with n-butyl bromide and t-butyl bromide. Reduction of 7 and 8 with lithium under sonication gives the respective 3-silolenide 2,5-carbodianions {[Ph4C4Si(n-Bu)2]−2•2[Li]+ (10) and [Ph4C4Si(t-Bu)2]−2•2[Li]+ (11)}, which are characterized by 1H-, 13C-, and 29Si-NMR spectroscopy. Polarization of phenyl groups in 3 is compared with those of silole anion/dianion, germole anion/dianion, and 3-silolenide 2,5-carbodianions 10 and 11.
Keywords: silacyclopentadiene; silole; anion; dianion; silyation; 3-silolenide; aromaticity; NMR
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MDPI and ACS Style

Hong, J.-H. Synthesis and NMR-Study of 1-Trimethylsilyl Substituted Silole Anion [Ph4C4Si(SiMe3)]•[Li]+ and 3-Silolenide 2,5-carbodianions {[Ph4C4Si(n-Bu)2]2•2[Li]+, [Ph4C4Si(t-Bu)2]2•2[Li]+} via Silole Dianion [Ph4C4Si]2•2[Li]+. Molecules 2013, 18, 10568-10579.

AMA Style

Hong J-H. Synthesis and NMR-Study of 1-Trimethylsilyl Substituted Silole Anion [Ph4C4Si(SiMe3)]•[Li]+ and 3-Silolenide 2,5-carbodianions {[Ph4C4Si(n-Bu)2]2•2[Li]+, [Ph4C4Si(t-Bu)2]2•2[Li]+} via Silole Dianion [Ph4C4Si]2•2[Li]+. Molecules. 2013; 18(9):10568-10579.

Chicago/Turabian Style

Hong, Jang-Hwan. 2013. "Synthesis and NMR-Study of 1-Trimethylsilyl Substituted Silole Anion [Ph4C4Si(SiMe3)]•[Li]+ and 3-Silolenide 2,5-carbodianions {[Ph4C4Si(n-Bu)2]2•2[Li]+, [Ph4C4Si(t-Bu)2]2•2[Li]+} via Silole Dianion [Ph4C4Si]2•2[Li]+." Molecules 18, no. 9: 10568-10579.

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