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Description
Divalent lanthanide complexes are attractive single-electron reductants as their reactivity can be tuned by the nature of both the Ln(II) metal centre and the ligand. In this context, Ln(II) complexes have been actively investigated for the activation and transformation of small molecules. In particular, homogeneous complexes allowing the activation and valorisation of CO under mild conditions are highly desirable. To date, only a limited number of systems has been able to promote the reductive coupling of CO molecules, and includes a handful of low-valent f block complexes.[1] For example, the well-studied divalent samarium complex [Cp*2Sm(THF)2] mediates CO reductive trimerisation.[2]
Using a highly reductive and sterically hindered Tm(II) complex, selective CO reductive dimerisation or trimerisation was achieved depending on the experimental conditions.[3] Further functionalisation reactions were performed using CO2 and other C=O electrophiles, resulting in the formation of novel oxygenated multicarbon products,[3] as well as original cycloaddition products.[4]
References
[1] R. Y. Kong, M. R. Crimmin, Dalton Trans. 2020, 49, 16587.
[2] W. J. Evans, J. W. Grate, L. A. Hughes, H Zhang, J. L. Atwood, J. Am. Chem. Soc. 1985, 107, 3728
[3] T. Simler, K. N. McCabe, L. Maron, G. Nocton, Chem. Sci. 2022, 13, 7449.
[4] N. Mahieu, C. Tillous Oliva, N. Casaretto, G. Nocton ,T. Simler, Manuscript in preparation.
