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Redox-Switchable Behavior of Transition-Metal Complexes Supported by Amino-Decorated N-Heterocyclic Carbenes
| Content Provider | MDPI |
|---|---|
| Author | Vincent, César Ruamps, Mirko Bastin, Stéphanie Rechignat, Lionel Sournia-Saquet, Alix Vendier, Laure Lugan, Noël Mouesca, Jean-Marie Valyaev, Dmitry A. Maurel, Vincent |
| Copyright Year | 2022 |
| Description | The coordination chemistry of the N-heterocyclic carbene ligand $IMes^{(NMe2)2}$, derived from the well-known IMes ligand by substitution of the carbenic heterocycle with two dimethylamino groups, was investigated with $d^{6}$ [Mn(I), Fe(II)], $d^{8}$ [Rh(I)], and $d^{10}$ [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 $[CuCl(IMes^{(NMe2)2}$)], $[RhCl(COD)(IMes^{(NMe2)2}$)], and $[FeCp(CO)_{2}$ (IMes^{(NMe2)2}$)](BF_{4}$) 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 $[MnCp(CO)_{2}$ $((IMes^{(NMe2)2}$)] 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. |
| Starting Page | 3776 |
| e-ISSN | 14203049 |
| DOI | 10.3390/molecules27123776 |
| Journal | Molecules |
| Issue Number | 12 |
| Volume Number | 27 |
| Language | English |
| Publisher | MDPI |
| Publisher Date | 2022-06-11 |
| Access Restriction | Open |
| Subject Keyword | Molecules Inorganic Chemistry Redox-active Ligands N-heterocyclic Carbene Organometallic Complexes Epr Spectroscopy Dft Calculations |
| Content Type | Text |
| Resource Type | Article |
