文摘
Treatment of [M(Bn)] (M = K, Cs) with [HC{C(But)NDipp}{C(But)NHDipp}] (LButH; Dipp = 2,6-diisopropylphenyl) afforded [K(LBut)(THF)n], 1, and [Cs(LBut)], 2, which were crystallized from hexane or benzene to afford [K(LBut)(THF)3], 1a, and [{Cs(LBut)}{Cs(LBut)(畏3-C6D6)}路C6D6]鈭?/sub>, 2a, respectively. Complexes 1 and 2 were utilized in the preparation of the previously reported [U(LBut)Cl3], which was cleanly converted to [U(LBut)I3], 3, via reaction with an excess of Me3SiI. Attempts to prepare U(III) complexes incorporating the LBut ligand proved unsuccessful, but utilizing [HC{C(Me)NDipp}{C(Me)NHDipp}] (LMeH) led to the isolation of [U(LMe)I2(THF)2], 4, via the reaction of [K(LMe)] with [U(I)3(THF)4]. Complex 4 can be derivatized via reaction with [K(Cp*)] (Cp* = 畏5-C5Me5) or [K{N(SiMe3)2}] to afford [U(LMe)(Cp*)I], 5, and [U(LMe){N(SiMe3)2}I], 6, respectively. The reaction of 4 with two equivalents of [K{N(SiMe3)2}] did not afford [U(LMe){N(SiMe3)2}2] as expected, but instead led to the isolation of the U(IV) species [U{HC[C(Me)NDipp][C(CH2)NDipp]}{N(SiMe3)2}2], 7, via deprotonation of the LMe ligand. The reduction of 4 with KC8 in benzene afforded the diuranium inverse sandwich complex [{U(LMe)I}2(渭-畏6:畏6-C6H6)], 8, albeit in low yield. Complexes 1鈥?b>8 have been characterized by single-crystal X-ray diffraction studies, by multielement NMR spectroscopy, and variously by FTIR spectroscopy, elemental analysis, UV/vis/NIR spectroscopy, and solution-state magnetic studies.
