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Isolation Of Transient Acyclic Germanium(I) Radicals Stabilized By Cyclic Alkyl(amino) Carbenes.

Mujahuddin M. Siddiqui, Samir Kumar Sarkar, Soumen Sinhababu, Paul Niklas Ruth, R. Herbst-Irmer, D. Stalke, Munmun Ghosh, Mingxing Fu, Lili Zhao, D. Casanova, G. Frenking, B. Schwederski, W. Kaim, H. Roesky
Published 2019 · Chemistry, Medicine

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Despite the notable progress in the stabilization of main group radicals by NHCs and cAACs, no germanium radicals have been isolated so far due to synthetic challenges. Stabilization of neutral [:EIR]• (E = Si, Ge) radicals is an uphill task, as these reactive transient species are highly susceptible to dimerization. Herein, we report the synthesis of acyclic neutral germanium(I) radicals Cy-cAAC:GeN(SiMe3)Dip (1) and Me-cAAC:GeN(SiPh3)Mes (2) obtained by the reduction of [Ar(SiR3)NGeCl3] with KC8 in the presence of cAAC. Compounds 1 and 2 are well characterized by single crystal X-ray structural analysis, cyclic voltammetry, and EPR spectroscopy. Furthermore, the structure and bonding of compounds 1 and 2 have been investigated by theoretical methods.



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