Syntheses, spectroscopic, redox, and structural properties of homoleptic Iron(III/II) dithione complexes

The quest for simple ligands to participate in concerted base metal-ligand multiple-electron redox events is driven by perspectives of replacing noble metals in catalysis and for discovering novel chemical reactivity. Yet the vast majority of simple ligand systems displays electrochemical potentials impractical for catalytic cycles substantiating the importance of new strategies towards aligned metal–ligand orbital energy levels. We herein demonstrate the possibility to establish and tame the elusive non-innocence of the ubiquitous acetylacetonate (acac), that is the most commonly employed anionic, chelating ligand towards elements across the entire Periodic Table. By employing the ligand field in the high-spin Cr(II) as a thermodynamic switch, we were able to chemically tailor the occurrence of metal–ligand redox events. The very mechanism can be understood as a destabilization of the dz2 orbital relative to the pi* LUMO of acac, which proffers a generalizable strategy to synthetically engineer non-innocence with seemingly redox-inactive ligands.

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Differences in actinide metal–ligand orbital interactions: comparison of U(iv) and Pu(iv) β-ketoiminate N,O donor complexes

Chemical Communications ◽

10.1039/c1cc12409a ◽

2011 ◽

Vol 47 (27) ◽

pp. 7647 ◽

Cited By ~ 23

Author(s):

David D. Schnaars ◽

Enrique R. Batista ◽

Andrew J. Gaunt ◽

Trevor W. Hayton ◽

Iain May ◽

...

Keyword(s):

Orbital Interactions ◽

Ligand Orbital ◽

Metal Ligand

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Mechanistic Insights into Co and Fe Quaterpyridine-Based CO2 Reduction Catalysts: Metal–Ligand Orbital Interaction as the Key Driving Force for Distinct Pathways

Journal of the American Chemical Society ◽

10.1021/jacs.0c09380 ◽

2021 ◽

Author(s):

Matthias Loipersberger ◽

Delmar G. A. Cabral ◽

Daniel B. K. Chu ◽

Martin Head-Gordon

Keyword(s):

Driving Force ◽

Co2 Reduction ◽

Orbital Interaction ◽

Ligand Orbital ◽

Reduction Catalysts ◽

Metal Ligand

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Ligand Field-Actuated Non-Innocence of Acetylacetonate

10.26434/chemrxiv.12052884.v1 ◽

2020 ◽

Author(s):

Morten Gotthold Vinum ◽

Laura Voigt ◽

Steen Hansen ◽

Colby Bell ◽

Kensha Marie Clark ◽

...

Keyword(s):

Noble Metals ◽

Chemical Reactivity ◽

Energy Levels ◽

Orbital Energy ◽

Ligand Field ◽

Ligand Orbital ◽

Catalytic Cycles ◽

Electrochemical Potentials ◽

New Strategies ◽

Metal Ligand

The quest for simple ligands to participate in concerted base metal-ligand multiple-electron redox events is driven by perspectives of replacing noble metals in catalysis and for discovering novel chemical reactivity. Yet the vast majority of simple ligand systems displays electrochemical potentials impractical for catalytic cycles substantiating the importance of new strategies towards aligned metal–ligand orbital energy levels. We herein demonstrate the possibility to establish and tame the elusive non-innocence of the ubiquitous acetylacetonate (acac), that is the most commonly employed anionic, chelating ligand towards elements across the entire Periodic Table. By employing the ligand field in the high-spin Cr(II) as a thermodynamic switch, we were able to chemically tailor the occurrence of metal–ligand redox events. The very mechanism can be understood as a destabilization of the dz2 orbital relative to the pi* LUMO of acac, which proffers a generalizable strategy to synthetically engineer non-innocence with seemingly redox-inactive ligands.

Download Full-text