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

Abstract

Reaction of [U(Tren(TIPS) )(THF)][BPh4 ] (1; Tren(TIPS) =N{CH2 CH2 NSi(iPr)3 }3 ) with NaPH2 afforded the novel f-block terminal parent phosphide complex [U(Tren(TIPS) )(PH2 )] (2; U-P=2.883(2) Å). Treatment of 2 with one equivalent of KCH2 C6 H5 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) Å). DFT calculations reveal a polarized-covalent UP bond with a Mayer bond order of 1.92.