Issue 25, 2022

CO reductive oligomerization by a divalent thulium complex and CO2-induced functionalization

Abstract

The divalent thulium complex [Tm(Cpttt)2] (Cpttt = 1,2,4-tris(tert-butyl)cyclopentadienyl) reacts with CO to afford selective CO reductive dimerization and trimerization into ethynediolate (C2) and ketenecarboxylate (C3) complexes, respectively. DFT calculations were performed to shed light on the elementary steps of CO homologation and support a stepwise chain growth. The attempted decoordination of the ethynediolate fragment by treatment with Me3SiI led to dimerization and rearrangement into a 3,4-dihydroxyfuran-2-one complex. Investigation of the reactivity of the C2 and C3 complexes towards other electrophiles led to unusual functionalization reactions: while the reaction of the ketenecarboxylate C3 complex with electrophiles yielded new multicarbon oxygenated complexes, the addition of CO2 to the ethynediolate C2 complex resulted in the formation of a very reactive intermediate, allowing C–H activation of aromatic solvents. This original intermolecular reactivity corresponds to an unprecedented functionalization of CO-derived ligands, which is induced by CO2.

Graphical abstract: CO reductive oligomerization by a divalent thulium complex and CO2-induced functionalization

Supplementary files

Article information

Article type
Edge Article
Submitted
29 Mar 2022
Accepted
06 May 2022
First published
09 May 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2022,13, 7449-7461

CO reductive oligomerization by a divalent thulium complex and CO2-induced functionalization

T. Simler, K. N. McCabe, L. Maron and G. Nocton, Chem. Sci., 2022, 13, 7449 DOI: 10.1039/D2SC01798A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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