Cerium(III) yldiide complexes with divergent CO reactivity

Alexander J. Gremillion; Hemant Kumar; Iker Del Rosal; Steven P. Kelley; Laurent Maron; Viktoria H. Gessner; Justin R. Walensky

doi:10.1039/D4CC04562A

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Cerium(iii) yldiide complexes with divergent CO reactivity†

Alexander J. Gremillion,^a Hemant Kumar,^a Iker Del Rosal,^b Steven P. Kelley,

^a Laurent Maron,

*^b Viktoria H. Gessner

*^c and Justin R. Walensky

*^a

Author affiliations

* Corresponding authors

^a Department of Chemistry, University of Missouri, Columbia, MO 65211, USA
E-mail: walenskyj@missouri.edu

^b Université de Toulouse and CNRS, INSA, UPS, CNRS, UMR 5212, Toulouse 31077, France
E-mail: Laurent.maron@irsamc.ups-tlse.fr

^c Faculty of Chemistry and Biochemistry, Ruhr-University Bochum, 44801 Bochum, Germany
E-mail: viktoria.gessner@rub.de

Abstract

Synthesis of cerium yldiide complexes and their reactivity with CO is demonstrated. In the case of the sulphur-tethered yldiide, the ketenyl complex is formed with release of PPh₃, while Ph₃PCCO is formed along with a sulfinato ligand in the case of the tosyl-substituted yldiide. Computational analysis shows that this diverging reactivity is due to the stability of the two isomers in the first step of each mechanism.

This article is part of the themed collection: Small Molecule Transformations of Energy Relevance

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DOI: https://doi.org/10.1039/D4CC04562A
Article type: Communication
Submitted: 04 Sept. 2024
Accepted: 01 Dec. 2024
First published: 12 Dec. 2024
This article is Open Access

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Chem. Commun., 2025, Advance Article

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Cerium(III) yldiide complexes with divergent CO reactivity

A. J. Gremillion, H. Kumar, I. Del Rosal, S. P. Kelley, L. Maron, V. H. Gessner and J. R. Walensky, Chem. Commun., 2025, Advance Article , DOI: 10.1039/D4CC04562A

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Chemical Communications

Cerium(iii) yldiide complexes with divergent CO reactivity†

Abstract

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Cerium(III) yldiide complexes with divergent CO reactivity

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