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）加入四氢呋喃（tetrahydrofuran，THF）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），可生成铀(IV)硫化物配合物[K(18-冠-6)][U(S)(NR₂)₃]（化合物1）与格默尔二聚体（Gomberg’s dimer）。类似地，将三苯甲基氧基钾（KOCPh3）加入四氢呋喃中的[U(NR₂)₃]体系中，随后加入18-冠-6，可生成铀(IV)氧化物配合物[K(18-冠-6)][U(O)(NR₂)₃]（化合物3）。该转化过程中还同时生成了三苯甲基阴离子配合物[K(18-冠-6)(THF)₂][CPh₃]（化合物5）与铀(IV)烷氧基配合物[U(OCPh₃)(NR₂)₃]（化合物4）。