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Reductive Cyclotrimerization of Carbon Monoxide to the Deltate Dianion by an Organometallic Uranium Complex
journal contribution
posted on 2023-06-08, 08:05 authored by Owen T Summerscales, Geoff Cloke, Peter B Hitchcock, Jennifer C Green, Nilay HazariDespite the long history of the Fischer-Tropsch reaction, carbon monoxide has proven remarkably resistant to selective homologation under mild conditions. Here, we find that an organouranium(III) complex induces efficient reductive trimerization of carbon monoxide at room temperature and pressure. The result is a triangular, cyclic C3O32-, or deltate, dianion held between two uranium(IV) units. The bonding within the C 3O32- unit and its coordination to the two U centers have been analyzed by x-ray diffraction and density functional theory computational studies, which show a stabilizing C-C agostic interaction between the C3 core and one U center. Solution nuclear magnetic resonance studies reveal a rapid equilibration of the deltate unit between the U centers.
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Publication status
- Published
Journal
ScienceISSN
0036-8075Publisher
Science (AAAS Publication)External DOI
Issue
5762Volume
311Page range
829-831Pages
3.0Department affiliated with
- Chemistry Publications
Notes
Main author; all experimental work done at Sussex; this paper describes an unprecedented reductive cyclotrimerisation of carbon monoxide to the aromatic deltate dianion, mediated by an organometallic complex; resulted in EPSRC Grant for a PDRA for 3 years; also highlighted in Science Perspective article, C&E News and Chemistry World.Full text available
- No
Peer reviewed?
- Yes
Legacy Posted Date
2012-02-06Usage metrics
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