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Synthesis, Structures, and Electronic Properties of Triple- and Double-Decker Ruthenocenes Incorporated by a Group 14 Metallole Dianion Ligand

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† Department of Chemistry, Graduate School of Science and Engineering, Saitama University, Shimo-okubo, Sakura-ku, Saitama 338-8570, Japan
‡ Fukui Institute for Fundamental Chemistry, Kyoto University, Takano-Nishihiraki-cho, Sakyo-ku, Kyoto 606-8103, Japan
§ Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan
[email protected]
Cite this: J. Am. Chem. Soc. 2014, 136, 37, 13059–13064
Publication Date (Web):August 22, 2014
https://doi.org/10.1021/ja507330p
Copyright © 2014 American Chemical Society
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Abstract

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The neutral triple-decker ruthenocenes and anionic ruthenocene bearing a stannole dianion were successfully synthesized by the reactions of dilithiostannoles with [Cp*RuCl]4. This is the first example of a transition-metal complex bearing a group 14 metallole dianion with μ–η5:η5 coordination mode. These complexes were fully characterized by NMR spectroscopy and single-crystal X-ray diffraction analysis. In the complexes, each of the ruthenium atoms is coordinated by the stannole ring in an η5-fashion. The aromaticity of the stannole dianion moieties is retained judging from no C–C bond alternation in the stannole rings. CH/π interaction was found in the packing structure of the SiMe3 derivative, which leads to a well-ordered column-like structure. The oxidation wave of the triple-decker complex was observed at −0.43 V (vs ferrocene), which reveals that the triple-decker type heavy ruthenocene is oxidized more easily than the ferrocene. Comparison of the oxidation potential between the triple-decker complex and decamethylruthenocene (Cp*2Ru, Cp* = η5-C5Me5) reveals that a stannole ligand functions as an electron-donating ligand much stronger than the conventional electron-rich Cp* ligand.

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Crystal data and CIF files of 2a, 2b, and 3b; 1H and 13C NMR spectra for 2a and 3b; Cartesian coordinates for 2a. This material is available free of charge via the Internet at http://pubs.acs.org.

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