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Reversible Insertion of CO into an Aluminium–Carbon Bond

preprint
submitted on 28.03.2019 and posted on 29.03.2019 by Richard Y Kong, Mark Crimmin
While reversible main-group mediated processes involving H2 and alkenes have been reported and studied for over a decade, no such reversible processes involving CO have been reported. In this paper, we show that a [2.2.1] aluminium metallobicycle is capable of reversibly inserting CO to form a [2.2.2] metallobicycle at 100 °C. Eyring analysis allowed determination of the Gibbs activation energy of the back-reaction, CO elimination reaction with G‡298K = 26.6 ±3.0 kcal mol-1. Computational studies reveal a highly asynchronous, but concerted, transition state for CO insertion. The coordination of CO to aluminium precedes C–C bond formation. The reversible migratory insertion reaction mimics that known for transition-metal and marks an important step forward for main group systems.

Funding

We are grateful to the Royal Society for provision of a University Research Fellowship (MRC) and the ERC (FluoroFix: 677367) for generous funding

History

Email Address of Submitting Author

m.crimmin@imperial.ac.uk

Institution

Imperial College London

Country

UK

ORCID For Submitting Author

0000-0002-9339-9182

Declaration of Conflict of Interest

Authors declare no conflict of interest

Version Notes

Version 1.0

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