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

Autor:	Liu Y; School of Chemistry, University of Nottingham, University Park Nottingham NG7 2RD UK Deborah.Kays@nottingham.ac.uk Nathan.Coles@nottingham.ac.uk., Coles NT; School of Chemistry, University of Nottingham, University Park Nottingham NG7 2RD UK Deborah.Kays@nottingham.ac.uk Nathan.Coles@nottingham.ac.uk., Cajiao N; Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford South Parks Road Oxford OX1 3QR UK.; Department of Chemistry, University of Rochester Rochester New York 14627 USA., Taylor LJ; School of Chemistry, University of Nottingham, University Park Nottingham NG7 2RD UK Deborah.Kays@nottingham.ac.uk Nathan.Coles@nottingham.ac.uk., Davies ES; School of Chemistry, University of Nottingham, University Park Nottingham NG7 2RD UK Deborah.Kays@nottingham.ac.uk Nathan.Coles@nottingham.ac.uk., Barbour A; School of Chemistry, University of Nottingham, University Park Nottingham NG7 2RD UK Deborah.Kays@nottingham.ac.uk Nathan.Coles@nottingham.ac.uk., Morgan PJ; School of Chemistry, University of Nottingham, University Park Nottingham NG7 2RD UK Deborah.Kays@nottingham.ac.uk Nathan.Coles@nottingham.ac.uk., Butler K; School of Chemistry, University of Nottingham, University Park Nottingham NG7 2RD UK Deborah.Kays@nottingham.ac.uk Nathan.Coles@nottingham.ac.uk., Pointer-Gleadhill B; School of Chemistry, University of Nottingham, University Park Nottingham NG7 2RD UK Deborah.Kays@nottingham.ac.uk Nathan.Coles@nottingham.ac.uk., Argent SP; School of Chemistry, University of Nottingham, University Park Nottingham NG7 2RD UK Deborah.Kays@nottingham.ac.uk Nathan.Coles@nottingham.ac.uk., McMaster J; School of Chemistry, University of Nottingham, University Park Nottingham NG7 2RD UK Deborah.Kays@nottingham.ac.uk Nathan.Coles@nottingham.ac.uk., Neidig ML; Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford South Parks Road Oxford OX1 3QR UK., Robinson D; Department of Chemistry and Forensics, School of Science and Technology, Nottingham Trent University Nottingham NG11 8NS UK., Kays DL; School of Chemistry, University of Nottingham, University Park Nottingham NG7 2RD UK Deborah.Kays@nottingham.ac.uk Nathan.Coles@nottingham.ac.uk.
Jazyk:	angličtina
Zdroj:	Chemical science [Chem Sci] 2024 May 07; Vol. 15 (25), pp. 9599-9611. Date of Electronic Publication: 2024 May 07 (Print Publication: 2024).
DOI:	10.1039/d4sc01286k
Abstrakt:	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 1 Mes to 4 Mes . Further studies past the formation of 4 Mes suggest that ketene complexes are formed en route to squaraine 2 Mes and iron carboxylate 3 Mes , 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. Competing Interests: There are no conflicts to declare. (This journal is © The Royal Society of Chemistry.)
Databáze:	MEDLINE
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