Triamidoamine-Uranium(IV)-Stabilized Terminal Parent Phosphide and Phosphinidene Complexes

摘要

Reaction of [U(Tren~(TIPS))(THF)][BPh4] (1; Tren~(TIPS) = N{CH2CH2NSi(iPr)3}3) with NaPH2 afforded the novel f-block terminal parent phosphide complex [U-(Tren~(TIPS))(PH2)] (2; U-P=2.883(2) A). Treatment of 2 with one equivalent of KCH2C6H5 and two equivalents of benzo-15-crown-5 ether (B15C5) afforded the unprecedented metal-stabilized terminal parent phosphinidene complex [U-(Tren~(TIPS))(PH)][K(B15C5)2] (4; U=P = 2.613(2) A). DFT calculations reveal a polarized-covalent U=P bond with a Mayer bond order of 1.92.