Crystalline Diuranium Phosphinidiide and μ‐Phosphido Complexes with Symmetric and Asymmetric UPU Cores

Reaction of [U(TrenTIPS )(PH2 )] (1, TrenTIPS =N(CH2 CH2 NSiPri3 )3 ) with C6 H5 CH2 K and [U(TrenTIPS )(THF)][BPh4 ] (2) afforded a rare diuranium parent phosphinidiide complex [{U(TrenTIPS )}2 (μ-PH)] (3). Treatment of 3 with C6 H5 CH2 K and two equivalents of benzo-15-crown-5 ether (B15C5) gave the diuranium μ-phosphido complex [{U(TrenTIPS )}2 (μ-P)][K(B15C5)2 ] (4). Alternatively, reaction of [U(TrenTIPS )(PH)][Na(12C4)2 ] (5, 12C4=12-crown-4 ether) with [U{N(CH2 CH2 NSiMe2 But )2 CH2 CH2 NSi(Me)(CH2 )(But )}] (6) produced the diuranium μ-phosphido complex [{U(TrenTIPS )}(μ-P){U(TrenDMBS )}][Na(12C4)2 ] [7, TrenDMBS =N(CH2 CH2 NSiMe2 But )3 ]. Compounds 4 and 7 are unprecedented examples of uranium phosphido complexes outside of matrix isolation studies, and they rapidly decompose in solution underscoring the paucity of uranium phosphido complexes. Interestingly, 4 and 7 feature symmetric and asymmetric UPU cores, respectively, reflecting their differing steric profiles.