Inorganic Chemistry · 2019 · 22 citations · 36 references
Anionic clusters with a homoatomic [Ge<sub>9</sub>] core are species with Ge atoms in low oxidation states. In this study their reaction with early-transition-metal complexes was investigated. We report the syntheses of Ti(III) complexes of silylated [Ge<sub>9</sub>] Zintl clusters, which are rare examples of molecular complexes with Ge-Ti interactions. The neutral species [Cp<sub>2</sub>(MeCN)Ti(η<sup>1</sup>-Ge<sub>9</sub>{Si(TMS)<sub>3</sub>}<sub>3</sub>)] (<b>1</b>) was obtained by the reaction of K[Ge<sub>9</sub>{Si(TMS)<sub>3</sub>}<sub>3</sub>] with [Cp<sub>2</sub>TiCl]<sub>2</sub> in toluene as dark orange crystals, whereas the reaction of K<sub>2</sub>[Ge<sub>9</sub>{Si(TMS)<sub>3</sub>}<sub>2</sub>] with [Cp<sub>2</sub>TiCl]<sub>2</sub> in thf and subsequent recrystallization from toluene resulted in dark green crystals of K<sub>3</sub>[Cp<sub>2</sub>Ti(η<sup>1</sup>-Ge<sub>9</sub>{Si(TMS)<sub>3</sub>}<sub>2</sub>)<sub>2</sub>] (<b>2</b>). Compound <b>2</b> contains the trianion [Cp<sub>2</sub>Ti(η<sup>1</sup>-Ge<sub>9</sub>{Si(TMS)<sub>3</sub>}<sub>2</sub>)<sub>2</sub>]<sup>3-</sup> (<b>2a</b>), which can be described either as a [Cp<sub>2</sub>Ti]<sup>+</sup>-bridged [Ge<sub>9</sub>{Si(TMS)<sub>3</sub>}<sub>2</sub>]<sup>2-</sup> dimer or as a heavily distorted tetrahedral Ti(III) complex bearing two germanide cluster ligands. Both compounds display donor-acceptor interactions between single Ge vertex atoms of the [Ge<sub>9</sub>] clusters and Ti(III). Compounds <b>1</b> and <b>2</b> were characterized by single-crystal X-ray diffraction, EPR spectroscopy, and elemental analysis.
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Chemistry of Deltahedral Zintl Ions
Slavi C. Sevov, José M. Goicoechea · Organometallics · 2006 · 285 citations