Pseudo electron-deficient organometallics: limited reactivity towards electron-donating ligands
dc.contributor.author | Pitto-Barry, Anaïs | * |
dc.contributor.author | Lupan, A. | * |
dc.contributor.author | Zegke, Markus | * |
dc.contributor.author | Swift, Thomas | * |
dc.contributor.author | Attia, A.A.A. | * |
dc.contributor.author | Lord, Rianne M. | * |
dc.contributor.author | Barry, Nicolas P.E. | * |
dc.date.accessioned | 2017-09-12T09:02:31Z | |
dc.date.available | 2017-09-12T09:02:31Z | |
dc.date.issued | 2017 | |
dc.identifier.citation | 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. | en_US |
dc.identifier.uri | http://hdl.handle.net/10454/13140 | |
dc.description | Yes | en_US |
dc.description.abstract | 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. | en_US |
dc.language.iso | en | en_US |
dc.rights | © 2017 Royal Society of Chemistry. Full-text reproduced in accordance with the publisher’s self-archiving policy. | en_US |
dc.subject | Organometallics; Half-sandwich metal complexes; Electron-deficient ligands | en_US |
dc.title | Pseudo electron-deficient organometallics: limited reactivity towards electron-donating ligands | en_US |
dc.status.refereed | Yes | en_US |
dc.date.Accepted | 2017-08-31 | |
dc.date.Accepted | 2018-09-20 | |
dc.date.application | 2017-09-19 | |
dc.type | Article | en_US |
dc.type.version | Accepted Manuscript | en_US |
dc.identifier.doi | https://doi.org/10.1039/C7DT02827J |