Several synthetic procedures have been developed for the preparation of early actinide aryloxide complexes. Simple alcoholysis of the actinide metallacycle [l brace][(Me[sub 3]Si)[sub 2]N][sub 2][ovr An(CH[sub 2]SiMe[sub 2]N]SiMe[sub 3])[r brace] [An = Th (1), U (2)] using 1 equiv of 2,6-disubstituted phenol results in the protonation of the An-C bond to form mono(aryloxide) complexes An(O-2,6-R[sub 2]C[sub 6]H[sub 3])[N(SiMe[sub 3])[sub 2]][sub 3] [An = U; R = t-Bu (3), i-Pr (4). An = Th; R = t-Bu (5), Me (6)] in essentially quantitative yield. For An = Th, further stepwise substitution products, the bis(aryloxide) or tris(aryloxide) complexes Th(O-2,6-t-Bu[sub 2]C[sub 6]H[sub 3])[sub 2][N(SiMe[sub 3])[sub 2]][sub 2] (7) and Th(O-2,6-t-Bu[sub 2]C[sub 6]H[sub 3])[sub 3][N(SiMe[sub 3])[sub 2]] (8), are readily isolated depending on the stoichiometry of added phenol. Prolonged (36 h) reflux with excess 2,6-di-tert-butylphenol fails to provide the homoleptic Th(O-2,6-t-Bu[sub 2]C[sub 6]H[sub 3])[sub 4] via this simple protonolysis reaction. Thorium metallacycle 1 reacts with 4 equiv of HO-4-t-BuC[sub 6]H[sub 4] to produce polymeric [Th(O-4-t-BuC[sub 6]H[sub 4])[sub 4]][sub x], addition of pyridine to which yields the monomeric adduct Th(O-4-t-BuC[sub 6]H[sub 4])[sub 4](py)[sub 3] (10). For alcoholysis reactions employing the uranium metallacycle (2), addition of slightly greater than 4 equiv of HO-2,6-t-Bu[sub 2]C[sub 6]H[sub 3]more » in refluxing toluene for 6 h provides U(O-2,6-R[sub 2]C[sub 6]H[sub 3])[sub 4] [R = t-Bu (11), i-Pr (12)]. While alcoholysis fails to provide the homoleptic Th(O-2,6-t-Bu[sub 2]C[sub 6]H[sub 3])[sub 4] (9), the authors can prepare this complex via a metathetical procedure. Reaction of ThI[sub 4](THF)[sub 4] with 4 equiv of KO-2,6-t-Bu[sub 2]C[sub 6]H[sub 3] in THF provides 9 in high yield.« less