Electrochemical Screening and DFT Analysis of Acetylacetonate Metal Complexes in Organic Solvents

Seven acetylacetonate (acac) metal complexes ranging from early transition metals to post-transition metals were examined by cyclic voltammetry in acetonitrile (MeCN), dichloromethane (DCM), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), and dimethylformamide (DMF). The electronic potential of any observed redox events is reported along with an analysis of the reversibility of those events across a range of scan rates. Group 8 compounds Fe(acac)3 Ru(acac)3 showed at least quasi-reversible reductions across all solvents while Ru(acac)3 also featured a reversible oxidation. The early and post-transition compounds VO(acac)2, Ga(acac)3 and In(acac)3 exhibited irreversible reductions, while TiO(acac)2 showed no redox activity within the examined potential ranges. Mn(acac)3 featured an oxidation that showed solvent-dependent reversibility, and a reduction that was irreversible in all examined solvents. DFT calculations indicated minimal solvent effects on the HOMO-LUMO gap for the majority of compounds, but a significant effect was observed for Ru(acac)3. This study serves as a valuable initial step for further examination of acetylacetonate metal complexes for applications as electrochemical internal standards, nanoparticle precursors, and electrocatalysts. Group 8 acetylacetonate complexes feature redox reversibility in organic solvents.Post transition metal complexes feature irreversible reductions in organic solvents.Density functional theory shows minimal solvent effects, save for ruthenium.