Chemical and redox non-innocence in low-valent molybdenum β diketonate complexes: novel pathways for CO₂ and CS₂ activation

The investigation of fundamental properties of low-valent molybdenum complexes bearing anionic ligands is crucial for elucidating the molybdenum's role in critical enzymatic systems involved in the transformation of small molecules, including the nitrogenase's iron molybdenum cofactor, FeMoco. The β-diketonate ligands in [Mo(acac)₃] (acac = acetylacetonate), one of the earliest low-valent Mo complexes reported, provide a robust anionic platform to stabilize Mo in its +III oxidation state. This complex played a key role in demonstrating the potential of low-valent molybdenum for small molecule activation, serving as the starting material for the preparation of the first reported molybdenum dinitrogen complex. Surprisingly however, given this fact and the widespread use of β-diketonate ligands in coordination chemistry, only a very limited number of low-valent Mo β-diketonate complexes have been reported. To address this gap, we explored the redox behavior of homoleptic molybdenum tris-β-diketonate complexes, employing a tertiary butyl substituted diketonate ligand (dipivaloylmethanate, ᵗᴮᵘdiket) to isolate and fully characterize the corresponding Mo complexes across three consecutive oxidation states (+IV, +III, +II). We observed marked reactivity of the most reduced congener with heterocumulenes CE₂ (E = O, S), yet with very distinct outcomes. Specifically, CO₂ stoichiometrically carboxylates one of the β-diketonate ligands, while in the presence of excess CS₂, catalytic reductive dimerization to tetrathiooxalate occurs. Through the isolation and characterization of reaction products and intermediates, we demonstrate that the observed reactivity results from the chemical non-innocence of the β-diketonate ligands, which facilitates the formation of a common ligand-bound intermediate, [Mo(ᵗᴮᵘdiket)₂(ᵗᴮᵘdiket·CE₂)]¹⁻ (E = O, S). The stability of this proposed intermediate dictates the specific reduction products observed, highlighting the relevance of the chemically non-innocent nature of β-diketonate ligands.