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Mechanistic investigations of the Fe(ii) mediated synthesis of squaraines

Liu, Yu; Coles, Nathan T.; Cajiao, Nathalia; Taylor, Laurence J.; Davies, E. Stephen; Barbour, Alistair; Morgan, Patrick J.; Butler, Kevin; Pointer-Gleadhill, Ben; Argent, Stephen P.; McMaster, Jonathan; Neidig, Michael L.; Robinson, David; Kays, Deborah L.

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Yu Liu

Nathalia Cajiao

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Teaching Associate in Organic Chemistry

E. Stephen Davies

Alistair Barbour

Patrick J. Morgan

Kevin Butler

Ben Pointer-Gleadhill

Michael L. Neidig

David Robinson

Professor of Inorganic Chemistry


The scission and homologation of CO is a fundamental process in the Fischer–Tropsch reaction. However, given the heterogeneous nature of the catalyst and forcing reaction conditions, it is difficult to determine the intermediates of this reaction. Here we report detailed mechanistic insight into the scission/homologation of CO by two-coordinate iron terphenyl complexes. Mechanistic investigations, conducted using in situ monitoring and reaction sampling techniques (IR, NMR, EPR and Mössbauer spectroscopy) and structural characterisation of isolable species, identify a number of proposed intermediates. Crystallographic and IR spectroscopic data reveal a series of migratory insertion reactions from 1Mes to 4Mes. Further studies past the formation of 4Mes suggest that ketene complexes are formed en route to squaraine 2Mes and iron carboxylate 3Mes, with a number of ketene containing structures being isolated, in addition to the formation of unbound, protonated ketene (8). The synthetic and mechanistic studies are supported by DFT calculations.

Journal Article Type Article
Acceptance Date May 4, 2024
Online Publication Date May 7, 2024
Publication Date 2024
Deposit Date May 28, 2024
Publicly Available Date May 30, 2024
Journal Chemical Science
Print ISSN 2041-6520
Electronic ISSN 2041-6539
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Public URL
Publisher URL


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