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

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Abstract

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.

Graphical abstract: Pseudo electron-deficient organometallics: limited reactivity towards electron-donating ligands

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Publication details

The article was received on 01 Aug 2017, accepted on 31 Aug 2017 and first published on 19 Sep 2017


Article type: Paper
DOI: 10.1039/C7DT02827J
Citation: Dalton Trans., 2017, Advance Article
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    Pseudo electron-deficient organometallics: limited reactivity towards electron-donating ligands

    A. Pitto-Barry, A. Lupan, M. Zegke, T. Swift, A. A. A. Attia, R. M. Lord and N. P. E. Barry, Dalton Trans., 2017, Advance Article , DOI: 10.1039/C7DT02827J

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