Isolation of a Uranium(III)-Carbon Multiple Bond Complex

Low-valent uranium-element multiple bond complexes remain scarce, though there is burgeoning interest regarding to their bonding and reactivity. Herein, isolation of a uranium(III)-carbon double bond complex [(Cp*)₂U(CDP)](BPh₄) (1) comprising a tridentate carbodiphosphorane (CDP) was reported for the first time. Oxidation of 1 afforded the corresponding U(IV) complex [(Cp*)₂U(CDP)](BPh₄)₂ (2). The distance between U and C in 2 is 2.481 Å, indicating the existence of a typical U=C double bond, which is further confirmed by quantum chemical calculations. Bonding analysis suggested that the CDP also serves as both σ- and π-donor in complex 1, though a longer U−C bond (2.666(3) Å) is observed. It implies that 1 is the first isolable mononuclear uranium(III) carbene complex. Moreover, these results suggest that CDPs are promising ligands to establish other low-valent f-block metal-carbon multiple bond complexes.