ZnH<sub>2</sub> as a Precursor to Catalytically ActiveRu–ZnH Heterometallic Complexes
Reaction of [Ru(IPr)<sub>2</sub>(CO)H][BAr<sup>F</sup><sub>4</sub>] (<b>1</b>; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; BAr<sup>F</sup><sub>4</sub> = B{3,5(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>}<sub>4</sub>) with an excess of ZnH<sub>2</sub> in THF gives the structurally characterized neutral Ru(ZnH) complex [Ru(IPr)<sub>2</sub>(CO)(ZnH)H<sub>3</sub>] (<b>6</b>) and Ru(ZnH)<sub>2</sub> salt [Ru(IPr)<sub>2</sub>(CO)(ZnH)<sub>2</sub>H<sub>3</sub>][BAr<sup>F</sup><sub>4</sub>] (<b>5</b>). Crystallographic and computational analyses show the presence of both bridging Ru–H–Zn hydrides and terminal Ru-hydrides in the two products. Calculations also identify a low-energy H/ZnH exchange pathway that rationalizes the experimentally observed (EXSY) fluxionality of the hydrides in <b>5</b>. At room temperature, this compound undergoes stoichiometric exchange with ZnMe<sub>2</sub> to give [Ru(IPr)<sub>2</sub>(CO)(ZnMe)<sub>2</sub>H<sub>3</sub>][BAr<sup>F</sup><sub>4</sub>] (<b>7</b>), and also proves to be catalytically active for the hydrogenation of 1-hexene and 5-hexene-2-one.
Publication Details
- Journal
- Figshare
- Published
- 2025-02-19
- DOI
- https://doi.org/10.1021/acs.inorgchem.4c05360.s001
- Primary Topic
- Organometallic Complex Synthesis and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 0.00