Reversible Insertion of CO into an Aluminium–Carbon Bond

29 March 2019, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


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.


Main Group Redox Catalysis
Migratory Insertion Reactions
Organometallic Chemistry
reaction mechanisms

Supplementary materials

ESI all 28thMarch


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.