Evidence for Non-Innocence of a β-Diketonate Ligand |
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| Authors: | Dr Morten Gotthold Vinum Laura Voigt Colby Bell Dmytro Mihrin Prof Dr René Wugt Larsen Prof Dr Kensha Marie Clark Prof Dr Kasper S Pedersen |
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| Institution: | 1. Department of Chemistry, Technical University of Denmark, Kemitorvet, Building 207, 2800 Kgs. Lyngby, Denmark;2. Department of Chemistry, Technical University of Denmark, Kemitorvet, Building 207, 2800 Kgs. Lyngby, Denmark
These authors contributed equally to this work.;3. Department of Chemistry, The University of Memphis, Memphis, TN USA |
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| Abstract: | β-Diketonates, such as acetylacetonate, are amongst the most common bidentate ligands towards elements across the entire periodic table and are considered wholly redox-inactive in their complexes. Herein we show that complexation of 1,1,1,5,5,5-hexafluoroacetylacetonate (hfac−) to CrII spontaneously affords CrIII and a reduced β-diketonate radical ligand scaffold, as evidenced by crystallographic analysis, magnetic measurements, optical spectroscopy, reactivity studies, and DFT calculations. The possibility of harnessing β-diketonates as electron reservoirs opens up possibilities for new metal–ligand concerted reactivity in the ubiquitous β-diketonate coordination chemistry. |
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| Keywords: | bidentate ligands chromium electronic structures magnetic properties non-innocent ligands |
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