Tin—Tin π Bonding as a Conduit for Alkali‐Metal Reduction
Reactions of the doubly reduced distannynes, [Ar'SnSnAr'M<sub>2</sub>], (Ar' = C<sub>6</sub>H<sub>3</sub>-2,6-Dipp; M = Li, Na, K), with the successively heavier group 1 elements (M') result in reduction of M and the isolation of [Ar'SnSnAr'M'<sub>2</sub>]. Although the viability of these observations, along with the reversible formation of [Ar'SnSnAr'K<sub>2</sub>] by treatment of [Ar'SnSnAr'Rb<sub>2</sub>] with potassium, is successfully predicted by a combined theoretical and thermochemical analysis, assessment of the bonding within [Ar'SnSnAr'M<sub>2</sub>] suggests that any M<sup>+</sup> ns valence orbital contribution should be too high in energy to effect M<sup>+</sup> reduction. Based on a consideration of the Sn─Sn π bonding and theoretical assessment of the resultant frontier orbitals, however, we suggest that the electron transfer necessary for M<sup>+</sup> reduction, occurs intramolecularly and via a suitably disposed π* SOMO of the putative radical anions, [Ar'SnSnAr'M<sub>2</sub>]<sup>•-</sup>.
Authors
- Kyle G. Pearce (ORCID: https://orcid.org/0000-0003-1886-4483)
- Michael S. Hill (ORCID: https://orcid.org/0000-0001-9784-9649)
- Agustín Morales (ORCID: https://orcid.org/0009-0006-8486-4149)
- Louis J. Morris (ORCID: https://orcid.org/0000-0003-2363-4498)
- Richards Emma
- Claire L. McMullin
Institutions
- University of Bath (GB)
- Cardiff University (GB)
- Cardiff Metropolitan University (GB)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2025-12-21
- DOI
- https://doi.org/10.1002/anie.202524068
- Citations
- 1
- Primary Topic
- Synthesis and characterization of novel inorganic/organometallic compounds
- Type
- article
- Field-Weighted Citation Impact
- 0.54
Funders
- Leverhulme Trust
- University of Bath
- Engineering and Physical Sciences Research Council