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Redox-Switchable Behavior of Transition-Metal Complexes Supported by Amino-Decorated N-Heterocyclic Carbenes.
- Source :
-
Molecules (Basel, Switzerland) [Molecules] 2022 Jun 11; Vol. 27 (12). Date of Electronic Publication: 2022 Jun 11. - Publication Year :
- 2022
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Abstract
- The coordination chemistry of the N-heterocyclic carbene ligand IMes <superscript>(NMe2)2</superscript> , derived from the well-known IMes ligand by substitution of the carbenic heterocycle with two dimethylamino groups, was investigated with d <superscript>6</superscript> [Mn(I), Fe(II)], d <superscript>8</superscript> [Rh(I)], and d <superscript>10</superscript> [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 <superscript>(NMe2)2</superscript> )], [RhCl(COD)(IMes <superscript>(NMe2)2</superscript> )], and [FeCp(CO) <subscript>2</subscript> (IMes <superscript>(NMe2)2</superscript> )](BF <subscript>4</subscript> ) 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) <subscript>2</subscript> ((IMes <superscript>(NMe2)2</superscript> )] 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.
Details
- Language :
- English
- ISSN :
- 1420-3049
- Volume :
- 27
- Issue :
- 12
- Database :
- MEDLINE
- Journal :
- Molecules (Basel, Switzerland)
- Publication Type :
- Academic Journal
- Accession number :
- 35744903
- Full Text :
- https://doi.org/10.3390/molecules27123776