{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Ruamps M"],"funding":["IR RENARD"],"pagination":["3776"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC9227367"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["27(12)"],"pubmed_abstract":["The coordination chemistry of the N-heterocyclic carbene ligand IMes<sup>(NMe2)2</sup>, derived from the well-known IMes ligand by substitution of the carbenic heterocycle with two dimethylamino groups, was investigated with d<sup>6</sup> [Mn(I), Fe(II)], d<sup>8</sup> [Rh(I)], and d<sup>10</sup> [Cu(I)] transition-metal centers. The redox behavior of the resulting organometallic complexes was studied through a combined experimental/theoretical study, involving electrochemistry, EPR spectroscopy, and DFT calculations. While the complexes [CuCl(IMes<sup>(NMe2)2</sup>)], [RhCl(COD)(IMes<sup>(NMe2)2</sup>)], and [FeCp(CO)<sub>2</sub> (IMes<sup>(NMe2)2</sup>)](BF<sub>4</sub>) exhibit two oxidation waves, the first oxidation wave is fully reversible but only for the first complex the second oxidation wave is reversible. The mono-oxidation event for these complexes occurs on the NHC ligand, with a spin density mainly located on the diaminoethylene NHC-backbone, and has a dramatic effect on the donating properties of the NHC ligand. Conversely, as the Mn(I) center in the complex [MnCp(CO)<sub>2</sub> ((IMes<sup>(NMe2)2</sup>)] is easily oxidizable, the latter complex is first oxidized on the metal center to form the corresponding cationic Mn(II) complex, and the NHC ligand is oxidized in a second reversible oxidation wave."],"journal":["Molecules (Basel, Switzerland)"],"pubmed_title":["Redox-Switchable Behavior of Transition-Metal Complexes Supported by Amino-Decorated N-Heterocyclic Carbenes."],"pmcid":["PMC9227367"],"funding_grant_id":["IR-RPE CNRS 3443"],"pubmed_authors":["Vendier L","Lugan N","Sournia-Saquet A","Bastin S","Valyaev DA","Cesar V","Ruamps M","Mouesca JM","Maurel V","Rechignat L"],"additional_accession":[]},"is_claimable":false,"name":"Redox-Switchable Behavior of Transition-Metal Complexes Supported by Amino-Decorated N-Heterocyclic Carbenes.","description":"The coordination chemistry of the N-heterocyclic carbene ligand IMes<sup>(NMe2)2</sup>, derived from the well-known IMes ligand by substitution of the carbenic heterocycle with two dimethylamino groups, was investigated with d<sup>6</sup> [Mn(I), Fe(II)], d<sup>8</sup> [Rh(I)], and d<sup>10</sup> [Cu(I)] transition-metal centers. The redox behavior of the resulting organometallic complexes was studied through a combined experimental/theoretical study, involving electrochemistry, EPR spectroscopy, and DFT calculations. While the complexes [CuCl(IMes<sup>(NMe2)2</sup>)], [RhCl(COD)(IMes<sup>(NMe2)2</sup>)], and [FeCp(CO)<sub>2</sub> (IMes<sup>(NMe2)2</sup>)](BF<sub>4</sub>) exhibit two oxidation waves, the first oxidation wave is fully reversible but only for the first complex the second oxidation wave is reversible. The mono-oxidation event for these complexes occurs on the NHC ligand, with a spin density mainly located on the diaminoethylene NHC-backbone, and has a dramatic effect on the donating properties of the NHC ligand. Conversely, as the Mn(I) center in the complex [MnCp(CO)<sub>2</sub> ((IMes<sup>(NMe2)2</sup>)] is easily oxidizable, the latter complex is first oxidized on the metal center to form the corresponding cationic Mn(II) complex, and the NHC ligand is oxidized in a second reversible oxidation wave.","dates":{"release":"2022-01-01T00:00:00Z","publication":"2022 Jun","modification":"2025-04-21T14:18:01.947Z","creation":"2025-04-21T14:18:01.947Z"},"accession":"S-EPMC9227367","cross_references":{"pubmed":["35744903"],"doi":["10.3390/molecules27123776"]}}