Pseudo electron-deficient organometallics: Limited reactivity towards electron-donating ligands

Pitto-Barry, Anaïs, Lupan, Alexandru, Zegke, Markus, Swift, Thomas, Attia, Amr A. A., Lord, Rianne M. ORCID: and Barry, Nicolas P. E. (2017) Pseudo electron-deficient organometallics: Limited reactivity towards electron-donating ligands. Dalton Transactions, 46. pp. 15676-15683. ISSN 1477-9226

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Half-sandwich metal complexes are of considerable interest in medicinal, material, and nanomaterial chemistry. The design of libraries of such complexes with particular reactivity and properties is therefore a major quest. Here, we report the unique and peculiar reactivity of eight apparently 16-electron half-sandwich metal (ruthenium, osmium, rhodium, and iridium) complexes based on benzene-1,2-dithiolato and 3,6-dichlorobenzene-1,2-dithiolato chelating ligands. These electron-deficient complexes do not react with electron-donor pyridine derivatives, even with the strong σ-donor 4-dimethylaminopyridine (DMAP) ligand. The Ru, Rh, and Ir complexes accept electrons from the triphenylphosphine ligand (σ-donor, π-acceptor), whilst the Os complexes were found to be the first examples of non-electron-acceptor electron-deficient metal complexes. We rationalised these unique properties by a combination of experimental techniques and DFT/TDFT calculations. The synthetic versatility offered by this family of complexes, the low reactivity at the metal center, and the facile functionalisation of the non-innocent benzene ligands is expected to allow the synthesis of libraries of pseudo electron-deficient half-sandwich complexes with unusual properties for a broad range of applications.

Item Type: Article
Faculty \ School: Faculty of Science > School of Chemistry
UEA Research Groups: Faculty of Science > Research Groups > Chemistry of Materials and Catalysis
Faculty of Science > Research Groups > Chemistry of Life Processes
Faculty of Science > Research Centres > Centre for Molecular and Structural Biochemistry
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Depositing User: LivePure Connector
Date Deposited: 30 Jan 2020 04:15
Last Modified: 22 Oct 2022 05:46
DOI: 10.1039/c7dt02827j

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