Reactivity of Diaryl Bismuth Cations toward a Platinum(0) Complex: Oxidative Aryl Transfer
Reactions of three aryl-substituted bismuth cations, [BiPh<sub>2</sub>(SbF<sub>6</sub>)], [BiMes<sub>2</sub>(SbF<sub>6</sub>)], and [BiDipp<sub>2</sub>(SbF<sub>6</sub>)], with the Pt<sup>0</sup> complex Pt-(PCy<sub>3</sub>)<sub>2</sub> have been investigated (Mes = 2,4,6-trimethyl-phenyl; Dipp = 2,6-di-<i>iso</i>-propyl-phenyl; Cy = cyclohexyl). Unexpectedly, and in contrast with the reactivity of the recently reported methyl analogue [BiMe<sub>2</sub>(SbF<sub>6</sub>)], the formation of isolable metal-only Lewis pairs [(Cy<sub>3</sub>P)<sub>2</sub>Pt→BiAr<sub>2</sub>(SbF<sub>6</sub>)] is not observed (Ar = aryl). Instead, an unprecedented bismuth-to-platinum oxidative aryl transfer is witnessed to give the Pt<sup>II</sup> complexes [PtAr-(PCy<sub>3</sub>)<sub>2</sub>(SbF<sub>6</sub>)], along with the suggested bismuthinidene intermediates BiAr. Attempts to trap these fleeting intermediates with an <i>ortho</i>-quinone led to a Pt<sup>II</sup> semiquinone radical complex.
Authors
- Crispin Lichtenberg (ORCID: https://orcid.org/0000-0002-0176-0939)
- Johannes Schwarzmann
- Cissie Slopianka
Institutions
- Philipps University of Marburg (DE)
Publication Details
- Journal
- Organometallics
- Published
- 2026-01-06
- DOI
- https://doi.org/10.1021/acs.organomet.5c00441
- Primary Topic
- Synthesis and characterization of novel inorganic/organometallic compounds
- Type
- article
- Field-Weighted Citation Impact
- 0.00