Mechanistic investigations of the Fe() mediated synthesis of squaraines
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...
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Published in | Chemical science (Cambridge) Vol. 15; no. 25; pp. 9599 - 9611 |
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Main Authors | , , , , , , , , , , , , , |
Format | Journal Article |
Language | English |
Published |
Cambridge
Royal Society of Chemistry
26.06.2024
The Royal Society of Chemistry |
Subjects | |
Online Access | Get full text |
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Summary: | 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.
In situ
monitoring and reaction sampling (IR, NMR, EPR, Mössbauer spectroscopy) and structural characterisation of isolable species allows detailed mechanistic insight into the scission/homologation of CO by two-coordinate iron terphenyl complexes. |
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Bibliography: | Electronic supplementary information (ESI) available. CCDC For ESI and crystallographic data in CIF or other electronic format see DOI https://doi.org/10.1039/d4sc01286k 2334282-2334296 ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 Authors contributed equally. |
ISSN: | 2041-6520 2041-6539 |
DOI: | 10.1039/d4sc01286k |