10.1021/ja507330p.s002 Takuya Kuwabara Takuya Kuwabara Jing-Dong Guo Jing-Dong Guo Shigeru Nagase Shigeru Nagase Takahiro Sasamori Takahiro Sasamori Norihiro Tokitoh Norihiro Tokitoh Masaichi Saito Masaichi Saito Synthesis, Structures, and Electronic Properties of Triple- and Double-Decker Ruthenocenes Incorporated by a Group 14 Metallole Dianion Ligand American Chemical Society 2014 stannole rings Electronic Properties oxidation wave stannole ring ruthenocene CH Group 14 Metallole Dianion LigandThe stannole dianion moieties ruthenium atoms SiMe 3 Cp ferrocene complex stannole dianion NMR spectroscopy group 14 metallole dianion stannole ligand functions 2014-09-17 00:00:00 Dataset https://acs.figshare.com/articles/dataset/Synthesis_Structures_and_Electronic_Properties_of_Triple_and_Double_Decker_Ruthenocenes_Incorporated_by_a_Group_14_Metallole_Dianion_Ligand/2254357 The neutral triple-decker ruthenocenes and anionic ruthenocene bearing a stannole dianion were successfully synthesized by the reactions of dilithiostannoles with [Cp*RuCl]<sub>4</sub>. This is the first example of a transition-metal complex bearing a group 14 metallole dianion with μ–η<sup>5</sup>:η<sup>5</sup> 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 η<sup>5</sup>-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 SiMe<sub>3</sub> 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*<sub>2</sub>Ru, Cp* = η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>) reveals that a stannole ligand functions as an electron-donating ligand much stronger than the conventional electron-rich Cp* ligand.