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.