Pseudo electron-deficient organometallics: limited reactivity towards electron-donating ligands
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2017Author
Pitto-Barry, AnaïsLupan, A.
Zegke, Markus
Swift, Thomas
Attia, A.A.A.
Lord, Rianne M.
Barry, Nicolas P.E.
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© 2017 Royal Society of Chemistry. Full-text reproduced in accordance with the publisher’s self-archiving policy.Peer-Reviewed
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Half-sandwich metal complexes are of considerable interest in medicine, 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 rationalized 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 functionalization 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 large range of applications.Version
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Pitto-Barry A, Lupan A, Zegke M et al (2017) Pseudo electron-deficient organometallics: limited reactivity towards electron-donating ligands. Dalton Transactions. 46(45): 15676-15683.Link to Version of Record
https://doi.org/10.1039/C7DT02827JType
Articleae974a485f413a2113503eed53cd6c53
https://doi.org/10.1039/C7DT02827J