Synthesis of Uranium–Ligand Multiple Bonds by Cleavage of a Trityl Protecting Group

Addition of KSCPh3 to [U­(NR2)3] (R = SiMe3) in tetrahydrofuran, followed by addition of 18-crown-6, results in formation of the U­(IV) sulfide, [K­(18-crown-6)]­[U­(S)­(NR2)3] (1) and Gomberg’s dimer. Similarly, addition of KOCPh3 to [U­(NR2)3] in tetrahydrofuran, followed by addition of 18-crown-6, results in formation of the U­(IV) oxide, [K­(18-crown-6)]­[U­(O)­(NR2)3] (3). Also observed in this transformation are the triphenylmethyl anion, [K­(18-crown-6)­(THF)2]­[CPh3] (5), and the U­(IV) alkoxide, [U­(OCPh3)­(NR2)3] (4).将三苯甲基硫代酸钾（KSCPh3）加入至四氢呋喃(tetrahydrofuran)中的[U(NR₂)₃]（R = 三甲基硅基SiMe₃）体系中，随后加入18-冠-6(18-crown-6)，可得到四价铀(U(IV))硫化物配合物[K(18-crown-6)][U(S)(NR₂)₃]（化合物1）与贡伯格二聚体(Gomberg’s dimer)。类似地，将三苯甲氧基钾（KOCPh3）加入至四氢呋喃中的[U(NR₂)₃]体系中，随后加入18-冠-6，可得到四价铀(U(IV))氧化物配合物[K(18-crown-6)][U(O)(NR₂)₃]（化合物3）。该转化过程中还会生成三苯甲基阴离子配合物[K(18-crown-6)(THF)₂][CPh₃]（化合物5）以及四价铀(U(IV))烷氧基配合物[U(OCPh3)(NR₂)₃]（化合物4）。