Zusammenfassung
Reaction of [U(Tren(TIPS))(PH2)] (1, Tren(TIPS)=N(CH(2)CH(2)NSiPri(3))(3)) with C6H5CH2K and [U(Tren(TIPS))(THF)][BPh4] (2) afforded a rare diuranium parent phosphinidiide complex [{U(Tren(TIP)S)}(2)(mu-PH)] (3). Treatment of 3 with C6H5CH2K and two equivalents of benzo-15-crown-5 ether (B15C5) gave the diuranium mu-phosphido complex [{U(Tren(TIPS))}2(mu-P)][K(B15C5)(2)] (4). Alternatively, ...
Zusammenfassung
Reaction of [U(Tren(TIPS))(PH2)] (1, Tren(TIPS)=N(CH(2)CH(2)NSiPri(3))(3)) with C6H5CH2K and [U(Tren(TIPS))(THF)][BPh4] (2) afforded a rare diuranium parent phosphinidiide complex [{U(Tren(TIP)S)}(2)(mu-PH)] (3). Treatment of 3 with C6H5CH2K and two equivalents of benzo-15-crown-5 ether (B15C5) gave the diuranium mu-phosphido complex [{U(Tren(TIPS))}2(mu-P)][K(B15C5)(2)] (4). Alternatively, reaction of [U(Tren(TIPS))(PH)][Na(12C(4))(2)] (5, 12C(4)=12-crown-4 ether) with [U{N(CH2CH2NSiMe2But)(2)CH2CH2NSi(Me)(CH2)(Bu-t)}] (6) produced the diuranium mu-phosphido complex [{U(Tren(TIPS))}(mu-P){U(Tren(DMBS))}][Na(12C(4))(2)] [7, Tren(DMBS)=N(CH2CH2NSiMe2But)(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.
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