The synthesis, chemical and structural characterization of a series of pentamethylcyclopentadienyl (Cp*) tantalum imido complexes and aryloxide derivatives are presented. Specifically, the imido complexes Cp*Ta(N
t
Bu)(CH2
R)2, where R = Ph [dibenzyl(tert-butylamido) (η5-pentamethylcyclopentadienyl)tantalum(IV) (1)], Me2Ph [tert-butylamido)bis(2-methyl-2-phenylpropyl) (η5-pentamethylcyclopentadienyl)tantalum(IV) (2)], CMe3 [(tert-butylamido)bis(2,2-dimethylpropyl) (η5-pentamethylcyclopentadienyl)tantalum(IV) (3)], are reported. The crystal structure of (3) reveals α-agostic interactions with the Ta atom. The resulting increase in the tantalum core coordination improves electronic stability. As such it does not react with pentafluorophenol, in contrast to the other two reported imido complexes [(1) and (2)]. Addition of C6F5OH to (1) yields a dimeric aryl-oxide derivative, [Cp*Ta(CH2Ph)(OC6H5)(μ-O)]2 [di-μ-oxido-bis[benzyl(pentafluorophenolato) (η5-pentamethylcyclopentadienyl)tantalum(V)] (4)]. Its crystal structure reveals long Ta—O(C6H5) bonds but short oxo-bridging Ta—O bonds. This is explained by accounting for the fierce electronic competition for the vacant d
π orbitals of the electrophilic TaV centre. Steric congestion around each metal is alleviated by a large twist angle (77.1°) between the benzyl and pentafluorophenyl ligands and the ordering of each of these groups into stacked pairs. The imido complex (2) reacts with C6F5OH to produce a mixture of Cp*Ta(OC6F5)4 [tetrakis(pentafluorophenolato)(η5-pentamethylcyclopentadienyl)tantalum(V) (5)] and [Cp*Ta(OC6F5)2(μ-O)]2 [di-μ-oxido-bis[bis(pentafluorophenolato)(η5-pentamethylcyclopentadienyl)tantalum(V)] (6)]. Steric congestion is offset in both cases by the twisting of its pentafluorophenyl ligands. Particularly strong electronic competition for the empty d
π metal orbitals in (6) is reflected in its bond geometry, and owes itself to the more numerous electron-withdrawing pentafluorophenyl ligands. The balance of steric and electronic factors affecting the reactivity of Cp* tantalum imido based complexes with pentafluorophenol is therefore addressed.