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

Abstract

AbstractThe 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(TrenTIPS)(OCP)] (TrenTIPS=N(CH2CH2NSiPri3)3) with KC8/2,2,2‐cryptand gives [{U(TrenTIPS)}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 OCP2−. 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.