Ligand field-actuated redox-activity of acetylacetonate

• Published in: Chemical science (Cambridge) 2020-08, Vol.11 (31), p.8267-8272
• Main Authors: Vinum, Morten Gotthold, Voigt, Laura, Hansen, Steen H, Bell, Colby, Clark, Kensha Marie, Larsen, René Wugt, Pedersen, Kasper S
• Format: Article
• Language: English
• Subjects: Actuation; Catalysis; Chemistry; Crystallography; Destabilization; Infrared spectroscopy; Ligands; Molecular orbitals; NMR; Noble metals; Nuclear magnetic resonance; Orbital stability; Transition metals; X ray powder diffraction
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/d0sc01836h

The quest for simple ligands that enable multi-electron metal-ligand redox chemistry is driven by a desire to replace noble metals in catalysis and to discover novel chemical reactivity. The vast majority of simple ligand systems display electrochemical potentials impractical for catalytic cycles, illustrating the importance of creating new strategies towards energetically aligned ligand frontier and transition metal d orbitals. We herein demonstrate the ability to chemically control the redox-activity of the ubiquitous acetylacetonate (acac) ligand. By employing the ligand field of high-spin Cr( ii ) as a switch, we were able to chemically tailor the occurrence of metal-ligand redox events via simple coordination or decoordination of the labile auxiliary ligands. The mechanism of ligand field actuation can be viewed as a destabilization of the d z 2 orbital relative to the π* LUMO of acac, which proffers a generalizable strategy to synthetically engineer redox-activity with seemingly redox-inactive ligands. Tailoring the chemical surroundings of chromium( ii ) allows reversible electron-transfer to the ubiquitous, purportedly redox-inactive acetylacetonate.