Non-redox reactivity of V() and Fe() formamidinates towards CO resulting in the formation of novel M() carbamates
Chemical fixation of CO 2 is a powerful tool for the preparation of novel multinuclear metal complexes and functional materials. Particularly, the insertion of CO 2 into a metal-X bond (X = H, C, N, O) often is a key elementary step in the various processes transforming this greenhouse gas into valu...
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| Published in | Dalton transactions : an international journal of inorganic chemistry Vol. 51; no. 43; pp. 16557 - 16564 |
|---|---|
| Main Authors | , , , , , |
| Format | Journal Article |
| Published |
08.11.2022
|
| Online Access | Get full text |
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| Summary: | Chemical fixation of CO
2
is a powerful tool for the preparation of novel multinuclear metal complexes and functional materials. Particularly, the insertion of CO
2
into a metal-X bond (X = H, C, N, O) often is a key elementary step in the various processes transforming this greenhouse gas into valuable products. Herein, we report on the reactivity between CO
2
and V(
ii
) and Fe(
ii
) complexes supported by
N
,
N
′-bis(2,6-diisopropylphenyl)formamidinate ligands (DippF). The reactions proceeded with multiple insertions of CO
2
into the M-N bonds leading to the isolation of three novel complexes: [(κ
2
-DippFCO
2
)(THF)V(μ-DippFCO
2
)
3
V(THF)], [(κ
2
-DippFCO
2
)Fe(μ-DippFCO
2
)
2
(μ-DippF)Fe(THF)] and [(κ
2
-DippFCO
2
)Fe(μ-DippFCO
2
)
3
Fe(κ
1
-DippFH)], which were characterised using single-crystal X-ray diffraction, FTIR and
57
Fe Mössbauer spectroscopy (for the diiron compounds). We provide the first well-documented studies of the CO
2
reactivity towards the V-N bond and broaden the state-of-the-art of the undeveloped area of the reactivity of low-valent V(
ii
) complexes. Moreover, we showed that the effectivity of the examined CO
2
insertion processes strongly depends on the used solvent's characteristics (for the Fe(
ii
) system) and the metal centre's coordination sphere geometry (for the V(
ii
) system).
Multiple CO
2
insertions into the M-N bonds of V(
ii
) and Fe(
ii
) bis(formamidinates) led to the isolation of three novel carbamates. The CO
2
insertion effectivity depended on the solvent used and the metal centre's coordination sphere geometry. |
|---|---|
| Bibliography: | 1 H NMR data. CCDC For ESI and crystallographic data in CIF or other electronic format see DOI https://doi.org/10.1039/d2dt02274e 2175762 and Electronic supplementary information (ESI) available: XRD, IR and 2161489-2161493 |
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/d2dt02274e |