The reaction of 2,6-di-adamantyl-4-R-phenol (Ar^ROH, R = Me, ^tBu) with ⁿBuLi in THF gave good yields of the lithiated derivatives (Ar^RO)Li(THF)₂. Addition of 2 equiv. of (Ar^RO)Li(THF)₂ to ZrCl₄(THF)₂ in THF afforded the base-free dichloride complexes (Ar^RO)ZrCl₂ (R = Me 1a, ^tBu 1b). The dibenzyl derivative (Ar^MeO)₂Zr(CH₂Ph)₂2 was synthesized by addition of 2 equiv. of PhCH₂MgCl to 1a in toluene. Reduction of the dichloride complexes 1a and 1b with KC₈ in toluene led to the formation of the toluene-bridged dizirconium complexes [(Ar^RO)₂Zr]₂(μ-η⁶:η⁶-C₇H₈) (R = Me 3a, ^tBu 3b). A similar reaction was carried out in benzene to produce the corresponding benzene-bridged analogue [(Ar^RO)₂Zr]₂(μ-η⁶:η⁶-C₆H₆) (R = Me 4a, ^tBu 4b). Treatment of 3a with 2 equiv. of 1-azidoadamantane (AdN₃) in THF resulted in the release of toluene and N₂, generating the monomeric imide complex (Ar^MeO)₂Zr(NAd)(thf) 5. When the analogous reaction was carried out in toluene, (Ar^MeO)₂Zr(AdNNNNAd) 6 was obtained. Structures of (Ar^RO)Li(THF)₂, 1a, 2 and 5 were determined by X-ray crystallography.