Terphenyl‐Ge as <i>μ</i><sub>2</sub>‐Ge‐bis(hexahapto‐Trip) Bridging Ligand to Form a New Transition Metal‐Only Chelating Lewis Base
Terphenylgermanium Ar*Ge [Ar*=C<sub>6</sub>H<sub>3</sub>(2,6-Trip)<sub>2</sub>, Trip=2,4,6-C<sub>6</sub>H<sub>2</sub>iPr<sub>3</sub>] was found to act as a novel μ<sub>2</sub>-Ge-bis(hexahapto-Trip) bridging ligand. Deprotonated terphenyl germanium trihydride [Li(thf)<sub>3</sub>][Ar*GeH<sub>2</sub>] (1) undergoes reductive elimination and transfer of hydrogen in reaction with dimeric [(COD)RhCl]<sub>2</sub> to yield the dinuclear complex [Ar*GeRh(COE)RhCl(COD)] (2). Subsequent chloride abstraction from compound 2 using Na[BAr<sup>F</sup> <sub>4</sub>] or Li[Al(O<sup>t</sup>Bu<sup>F</sup>)<sub>4</sub>] results in the cationic complexes [Ar*GeRh(COE)Rh(COD)][WCA] (3) {WCA: [BAr<sup>F</sup> <sub>4</sub>]<sup>-</sup> (Ar<sup>F</sup>=C<sub>6</sub>H<sub>3</sub>-3,5-(CF<sub>3</sub>)<sub>2</sub>), [Al(O<sup>t</sup>Bu<sup>F</sup>)<sub>4</sub>]<sup>-</sup>}. Ligand exchange of olefin for CO yields the carbonyl complex [Ar*Ge(Rh(CO))<sub>2</sub>][BAr<sup>F</sup> <sub>4</sub>] (4). In an alternative approach to the synthesis of carbonyl complex 4, [Li(thf)<sub>3</sub>][Ar*GeH<sub>2</sub>] (1) was treated with [Rh(CO)<sub>2</sub>Cl]<sub>2</sub> leading to the isolation of a hexanuclear rhodium cluster [(μ<sub>3</sub>-Ar*Ge)<sub>2</sub>{Rh(CO)<sub>2</sub>}<sub>6</sub>(μ<sub>3</sub>-H)<sub>2</sub>] (5) in reasonable yield. In reactions with [Rh(CO)<sub>2</sub>Cl]<sub>2</sub> or [Ph<sub>3</sub>PAuCl] complex 4 abstracts the chloride ligand and forms tetranuclear complexes featuring a GeRh<sub>3</sub>- or GeRh<sub>2</sub>Au-rectangle, [Ar*GeCl(Rh<sub>3</sub>(CO)<sub>4</sub>)][BAr<sup>F</sup> <sub>4</sub>] (6), or [Ar*GeCl{Rh<sub>2</sub>(CO)<sub>2</sub>}(AuPPh<sub>3</sub>)][BAr<sup>F</sup> <sub>4</sub>] (7).
Authors
- Hartmut Schubert
- Johanna Manegold
- Klaus Eichele (ORCID: https://orcid.org/0000-0002-9318-5782)
- Lars Wesemann (ORCID: https://orcid.org/0000-0003-4701-4410)
- Adrian Ebisch
Institutions
- Thüringer Universitäts- und Landesbibliothek (DE)
- University of Tübingen (DE)
Publication Details
- Journal
- Chemistry - A European Journal
- Published
- 2024-11-20
- DOI
- https://doi.org/10.1002/chem.202404201
- Citations
- 2
- Primary Topic
- Synthesis and characterization of novel inorganic/organometallic compounds
- Type
- article
- Field-Weighted Citation Impact
- 0.32