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

Abstract

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.