Allosteric Differentiation of Al(I) Reactivity
The dimeric potassium alumanyl, [{SiN<sup>Dipp</sup>}AlK]<sub>2</sub> ({SiN<sup>Dipp</sup>} = {CH<sub>2</sub>SiMe<sub>2</sub>N(Dipp)}<sub>2</sub>; Dipp = 2,6-i-Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>), reacts with two equivalents of PhC≡CR (R = Ph or SiMe<sub>3</sub>) with the exclusive formation of the aluminacyclopropene derivatives, [{SiN<sup>Dipp</sup>}Al{η<sup>2</sup>-C<sub>2</sub>(R<sup>1</sup>)(R<sup>2</sup>)}]. In contrast, reactions with an equal stoichiometry of both alumanyl and alkyne reagents provide the products of not only alkyne cycloaddition but also para-C-H activation of a phenyl substituent. Supported by a theoretical study, this outcome is judged to result from a sequence of cooperative steps and the introduction of a modicum of kinetic discrimination that is suggested to be allosteric in origin.
Authors
- Ryan J. Schwamm (ORCID: https://orcid.org/0000-0001-8025-231X)
- Henry Shere (ORCID: https://orcid.org/0000-0003-1487-2806)
- James A. Kenar (ORCID: https://orcid.org/0000-0001-8347-8496)
- Michael S. Hill (ORCID: https://orcid.org/0000-0001-9784-9649)
- Claire L. McMullin (ORCID: https://orcid.org/0000-0002-4924-2890)
- Mary F. Mahon (ORCID: https://orcid.org/0000-0002-8854-8040)
Institutions
- University of Bath (GB)
Publication Details
- Journal
- Chemistry - A European Journal
- Published
- 2025-04-11
- DOI
- https://doi.org/10.1002/chem.202501352
- Citations
- 4
- Primary Topic
- Organometallic Complex Synthesis and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 3.74
Funders
- University of Bath
- Engineering and Physical Sciences Research Council