Volume 42, Issue 10 pp. 1121-1127
Breaking Report

Heavier Group 14 Congeners of Metalla-isobenzenes: Access to Metalla-isosilabenzene and Metalla-isogermabenzene by One-Pot Reactions

Jinyu Zhao

Jinyu Zhao

Department of Chemistry, Xiamen University, Xiamen, Fujian, 361005 China

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Yapeng Cai

Yapeng Cai

Department of Chemistry, Xiamen University, Xiamen, Fujian, 361005 China

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Xin Yang

Xin Yang

Department of Chemistry, Xiamen University, Xiamen, Fujian, 361005 China

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Hong Zhang

Corresponding Author

Hong Zhang

Department of Chemistry, Xiamen University, Xiamen, Fujian, 361005 China

E-mail: [email protected]Search for more papers by this author
First published: 05 February 2024

Comprehensive Summary

Metalla-isosilabenzenes and metalla-isogermabenzenes have been successfully synthesized by the formal [5+1]-cycloaddition of diethynylsilane or diethynylgermane with simple metal complexes. This is the first example of a heavier Group 14 metalla-isobenzene isomer bearing a cumulative double bond motif within a metallacycle. These novel complexes were fully characterized by NMR spectroscopy and single-crystal X-ray diffraction analysis. The stabilization of the cyclic metal-vinylidene complexes has been analyzed using density functional theory (DFT) calculations. When the metalla-isosilabenzenes bearing Si—H bond were treated with the trityl salt as a hydride scavenger, the formation of silylium cation was observed spectroscopically. Both of metalla-isosilabenzenes and metalla-isogermabenzenes can readily undergo migratory insertion reactions to furnish siloles or germoles.image

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