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dc.contributor.authorPitto-Barry, Anaïs*
dc.contributor.authorLupan, A.*
dc.contributor.authorZegke, Markus*
dc.contributor.authorSwift, Thomas*
dc.contributor.authorAttia, A.A.A.*
dc.contributor.authorLord, Rianne M.*
dc.contributor.authorBarry, Nicolas P.E.*
dc.date.accessioned2017-09-12T09:02:31Z
dc.date.available2017-09-12T09:02:31Z
dc.date.issued2017
dc.identifier.citationPitto-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.en_US
dc.identifier.urihttp://hdl.handle.net/10454/13140
dc.descriptionYesen_US
dc.description.abstractHalf-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.en_US
dc.language.isoenen_US
dc.relation.isreferencedbyhttp://dx.doi.org/10.1039/C7DT02827J
dc.rights© 2017 Royal Society of Chemistry. Full-text reproduced in accordance with the publisher’s self-archiving policy.en_US
dc.subjectOrganometallics; Half-sandwich metal complexes; Electron-deficient ligandsen_US
dc.titlePseudo electron-deficient organometallics: limited reactivity towards electron-donating ligandsen_US
dc.status.refereedYesen_US
dc.date.Accepted2017-08-31
dc.date.Accepted2018-09-20
dc.date.application2017-09-19
dc.typeArticleen_US
dc.type.versionAccepted Manuscripten_US


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