The Reduction of Metallabenzenes: Different Scenarios Highly Dependent on the Central Group 14 Elements, Si vs. Ge.

Autor: Tsuji S; Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan., Tokitoh N; Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan.; Integrated Research Consortium on Chemical Sciences, Gokasho, Uji, Kyoto, 611-0011, Japan., Yamada H; Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan., Mizuhata Y; Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan.; Integrated Research Consortium on Chemical Sciences, Gokasho, Uji, Kyoto, 611-0011, Japan.
Jazyk: angličtina
Zdroj: Chemistry, an Asian journal [Chem Asian J] 2024 Jan 15; Vol. 19 (2), pp. e202300945. Date of Electronic Publication: 2023 Dec 11.
DOI: 10.1002/asia.202300945
Abstrakt: In order to synthesize a silabenzenyl anion, in which the anionic carbon atom of a phenyl anion was replaced with a silicon atom, the reductive dearylation reaction of 1-Tbt-2-tert-butyl-silabenzene (Tbt=2,4,6-tris[bis(trimethylsilyl)methyl]phenyl) with KC 8 was attempted. Unexpectedly, this reaction resulted in the formation of a dianion species without the elimination of the Tbt group. This is totally different from the reactions of Tbt-substituted germa- or stannabenzene with KC 8 , which resulted in the formation of the corresponding heavy analogues of phenyl anion, together with the elimination of Tbt group. Experimental and theoretical investigation revealed that one of the protons of the o-benzyl positions of the Tbt group was abstracted by the negatively charged silicon atom of an in-situ generated intermediate. Compared with the previously reported germanium system, the contrasting results indicate that the central heavy group 14 element has a great influence on the elimination step of the Tbt group.
(© 2023 Wiley-VCH GmbH.)
Databáze: MEDLINE
Externí odkaz: