Trapping of a Highly Bent and Reduced Form of 2-Phosphaethynolate in a Mixed-Valence Diuranium-Triamidoamine Complex

The chemistry of 2-phosphaethynolate is burgeoning, but there remains much to learn about this ligand, for example its reduction chemistry is scarce as this promotes P-C-O fragmentations or couplings. Here, we report that reduction of [U(Tren^TIPS )(OCP)] (Tren^TIPS =N(CH₂ CH₂ NSiPrⁱ ₃ )₃ ) with KC₈ /2,2,2-cryptand gives [{U(Tren^TIPS )}₂ {μ-η² (OP):η² (CP)-OCP}][K(2,2,2-cryptand)]. The coordination mode of this trapped 2-phosphaethynolate is unique, and derives from an unprecedented highly reduced and highly bent form of this ligand with the most acute P-C-O angle in any complex to date (P-C-O ∡ ≈127°). The characterisation data support a mixed-valence diuranium(III/IV) formulation, where backbonding from uranium gives a highly reduced form of the P-C-O unit that is perhaps best described as a uranium-stabilised OCP^2-. radical dianion. Quantum chemical calculations reveal that this gives unprecedented carbene character to the P-C-O unit, which engages in a weak donor-acceptor interaction with one of the uranium ions.