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Mercury-Substituted Silyl Radical Intermediates in Formation and Fragmentation of Geminal Dimercury

Summary: Mercury-Substituted Silyl Radical Intermediates in
Formation and Fragmentation of Geminal Dimercury
Silyl Compounds
Dmitry Bravo-Zhivotovskii,* Ilya Ruderfer, Michael Yuzefovich, Monica Kosa,
Mark Botoshansky, Boris Tumanskii, and Yitzhak Apeloig*
Department of Chemistry and Lise Meitner-Minerva Center for Computational Quantum
Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel
Received February 18, 2005
The first known trimercury and cyclic tetramercury organosilicon compounds containing
the -(Hg-R2Si-Hg)- fragment, (t-BuHgSiR2)2Hg [R ) i-Pr3Si (3a), R ) t-Bu2MeSi (3b)]
and [(i-Pr3Si)2SiHg]4 (6), were synthesized and characterized. Reactions of the corresponding
H2SiR2 silanes with t-Bu2Hg yielded 3a and 3b. 6 was obtained from a hexane solution of
3a that was stored at room temperature for 6 months. The molecular structures of 3a, 3b,
and 6 were determined by X-ray analysis. Photolysis and thermolysis of 3 leads to formation
of mercury-substituted silyl radicals (previously unknown). Their structure was confirmed
by a detailed EPR study and by trapping with 2,2,6,6,-tetramethyl-1-piperidinyloxyl (TEMPO)
radical. A radical mechanism for the formation of 3 was evidenced by the observation of
EPR signals in the reaction mixture of Hg-substituted silyl radicals.
Silylmercury compounds have been known since the


Source: Apeloig, Yitzhak - Department of Chemistry, Technion, Israel Institute of Technology


Collections: Chemistry