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Chemoselective C–C σ-Bond Activation of Biphenylene

preprint
revised on 01.09.2020 and posted on 01.09.2020 by Richard Y Kong, Mark Crimmin
The chemoselective cleavage of an arene ring in biphenylene is reported using an aluminium(I) complex. The reaction proceeds with complete integrity of the central 4-membered ring despite this ring containing the weakest C–C σ-bond in the hydrocarbon scaffold. A reaction intermediate derived from the (4+1) cycloaddition of the aluminium(I) complex to the p-system of biphenylene was isolated. Further experiments and DFT calculations suggest that this intermediate is involved in breaking of the C–C σ-bond. Activation strain analysis was used to understand the origins of the remarkable chemoselectivity of this system. Both the symmetry and diffuseness of the frontier molecular orbitals of the aluminium(I) fragment are implicated in its unusual reactivity with biphenylene.

Funding

Imperial College Presidents Scholarship (RYK)

History

Email Address of Submitting Author

m.crimmin@imperial.ac.uk

Institution

Imperial College London

Country

United Kingdom

ORCID For Submitting Author

0000-0002-9339-9182

Declaration of Conflict of Interest

No conflicts of interest.

Version Notes

Version 2 - Edits to references, summary and document template

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