Author: ["Liangchun Li","Tomohide Fukawa","Tsukasa Matsuo","Daisuke Hashizume","Hiroyuki Fueno","Kazuyoshi Tanaka","Kohei Tamao"]
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Abstract
The carbon–oxygen double bond of ketones (R2C=O) makes them among the most important organic compounds, but their homologues, heavy ketones with an E=O double bond (E = Si, Ge, Sn or Pb), had not been isolated as stable compounds. Their unavailability as monomeric molecules is ascribed to their high tendency for intermolecular oligomerization or polymerization via opening of the E=O double bond. Can such an intermolecular process be inhibited by bulky protecting groups? We now report that it can, with the first isolation of a monomeric germanium ketone analogue (Eind)2Ge=O (Eind = 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl), stabilized by appropriately designed bulky Eind groups, with a planar tricoordinate germanium atom. Computational studies and chemical reactions suggest the Ge=O double bond is highly polarized with a contribution of a charge-separated form (Eind)2Ge+−O−. The germanone thus exhibits unique reactivities that are not observed with ordinary ketones, including the spontaneous trapping of CO2 gas to provide a cyclic addition product. Heavier analogues of ketones — containing a double bond between a group 14 element and oxygen — have so far not been isolated as stable compounds. Now, a stable monomeric germanone with a highly polarized Ge=O double bond has been isolated, stabilized by rigid bulky ligands. Cite this article
Li, L., Fukawa, T., Matsuo, T. et al. A stable germanone as the first isolated heavy ketone with a terminal oxygen atom. Nature Chem 4, 361–365 (2012). https://doi.org/10.1038/nchem.1305 