Uranyl Coordination by the 14-Membered Macrocycle Dibenzotetramethyltetraaza[14]annulene.

Reaction of [UO(N(SiMe))(THF)] with 1 equiv of dibenzotetramethyltetraaza[14]annulene (tmtaaH) affords the uranyl complex [UO(tmtaaH)(N(SiMe)) (THF)] (1) (THF = tetrahydrofuran) as red blocks in 83% yield. Similarly, thermolysis of a mixture of [UO(N(SiMe))(THF)] and 2 equiv of tmtaaH affords [UO(tmtaaH)] (2), which can be isolated as red-orange crystals in 67% yield after workup. Both 1 and 2 were fully characterized, including analysis by X-ray crystallography. The tmtaaH ligands in 1 and 2 are only coordinated to the uranium center via one β-diketiminate fragment, while the protonated β-diketimine portion of the ligand remains uncoordinated. Reaction of [UO(N(SiMe))(THF)] with 1 equiv of Li(tmtaa) in CH results in the formation of [Li(THF)][UO(N(SiMe))(tmtaa)] (3), which can be isolated in 55% yield as a red-brown crystalline solid. The tmtaa ligand in complex 3 supports a dative interaction between an oxo ligand in the uranyl fragment and a lithium cation, suggesting that tmtaa could be a useful ligand for developing the oxo ligand functionalization chemistry of the uranyl ion.