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A stable germanone as the first isolated heavy ketone with a terminal oxygen atom

Nature Chemistry volume 4, pages 361–365 (2012)Cite this article

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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.

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Figure 1
Figure 2: Synthetic scheme for 1 and 2, together with the charge-separated canonical form 2′.
Figure 3: Molecular structures of 1 and 2.
Figure 4: Selected MOs and their energy levels (in eV) for 2, together with the chemical structure.
Figure 5: Electrostatic potential maps drawn by GaussView.
Figure 6: Reactions of 2.

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Acknowledgements

We thank the Ministry of Education, Culture, Sports, Science and Technology of Japan for the Grant-in-Aid for Specially Promoted Research (No. 19002008). The numerical calculations were performed, in part, at the Research Center for Computational Science, Okazaki, Japan. We thank Y. Hongo, T. Nakamura and S. Kamiguchi (RIKEN) for their help with the mass spectrometry and Raman spectroscopy. We thank the RIKEN materials characterization team for the elemental analyses of the samples synthesized in this study. We also thank N. Tokitoh and M. Driess for their valuable discussions.

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Authors and Affiliations

  1. Functional Elemento-Organic Chemistry Unit, RIKEN Advanced Science Institute, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan

    Liangchun Li, Tomohide Fukawa, Tsukasa Matsuo & Kohei Tamao

  2. Japan Science and Technology Agency, Precursory Research for Embryonic Science and Technology, 4-1-8 Honcho Kawaguchi, Saitama, 332-0012, Japan

    Tsukasa Matsuo

  3. Advanced Technology Support Division, RIKEN Advanced Science Institute, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan

    Daisuke Hashizume

  4. Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto, 615-8510, Japan

    Hiroyuki Fueno & Kazuyoshi Tanaka

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  1. Liangchun Li
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Contributions

L.L. and T.F. performed all the experiments. T.M. co-directed the project and designed the experiments. D.H. carried out the X-ray crystallographic analysis. H.F. and K. Tanaka performed the computational studies. K. Tamao directed the project. L.L., T.M. and K. Tamao co-wrote the paper. All authors contributed to discussions.

Corresponding authors

Correspondence to Tsukasa Matsuo or Kohei Tamao.

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Supplementary information

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Supplementary information (PDF 1529 kb)

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Crystallographic data for compound 1 (CIF 37 kb)

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Crystallographic data for compound 2 (CIF 36 kb)

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Crystallographic data for compound 3 (CIF 36 kb)

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Crystallographic data for compound 4 (CIF 46 kb)

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Crystallographic data for compound 5 (CIF 36 kb)

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Crystallographic data for compound 6 (CIF 44 kb)

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Crystallographic data for compound 7 (CIF 47 kb)

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Crystallographic data for compound 8 (CIF 23 kb)

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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

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