Flash Communication: Pd<sub>2</sub>Zn<sub>2</sub> Clusters from the Reduction of Palladium(II) Dichloride Precursors with Metallic Zinc
We report the synthesis and solid-state characterization of two unusual Pd<sub>2</sub>Zn<sub>2</sub> clusters formed from the partial reduction of [PdL<sub>2</sub>Cl<sub>2</sub>] precursors (L<sub>2</sub> = dcpe or dppe) with metallic zinc. The new clusters have been characterized by single crystal X-ray diffraction and contain a Pd<sub>2</sub>Zn<sub>2</sub>Cl<sub>3</sub> core capped by two chelating phosphine ligands with Zn in the formal +1.5 oxidation state. While they possess a near tetrahedral arrangement of metal ions, calculations and bonding analysis (NBO, AIM) suggest that there is limited Zn- - -Zn bonding in these species. Characterization in the solution state is suggestive of dynamic behavior on dissolution, with both diamagnetic and paramagnetic species observed by NMR and EPR spectroscopy. One of these Pd<sub>2</sub>Zn<sub>2</sub> clusters was shown to be an effective precursor for the homocoupling of an aryl bromide.
Authors
- Mark R. Crimmin (ORCID: https://orcid.org/0000-0002-9339-9182)
- Philip W. Miller (ORCID: https://orcid.org/0000-0002-8394-2516)
- Martí Garçon (ORCID: https://orcid.org/0000-0002-3214-0150)
- Georgina Rai
Institutions
- Imperial College London (GB)
Publication Details
- Journal
- Organometallics
- Published
- 2025-03-08
- DOI
- https://doi.org/10.1021/acs.organomet.4c00506
- Primary Topic
- Organometallic Complex Synthesis and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- GlaxoSmithKline
- Engineering and Physical Sciences Research Council