2-(Arylamino)-4,6-di-tert-butylphenols containing 4-substituted phenyl groups (^RapH₂) react with oxobis(ethylene glycolato)osmium(VI) in acetone to give square pyramidal bis(amidophenoxide)oxoosmium(VI) complexes. A mono-amidophenoxide complex is observed as an intermediate in these reactions. Reactions in dichloromethane yield the diolate (^Hap)₂Os(OCH₂CH₂O). Both the glycolate and oxo complex are converted to the corresponding cis-dichloride complex on treatment with chlorotrimethylsilane. The novel bis(aminophenol) ligand EganH₄, containing an ethylene glycol dianthranilate bridge, forms the chelated bis(amidophenoxide) complex (Egan)OsO, where the two nitrogen atoms of the tetradentate ligand bind in the trans positions of the square pyramid. Structural and spectroscopic features of the complexes are described well by an osmium(VI)-amidophenoxide formulation, with the amount of π donation from ligand to metal increasing markedly as the co-ligands change from oxo to diolate to dichloride. In the oxo-bis(amidophenoxides), the symmetry of the ligand π orbitals results in only one effective π donor interaction, splitting the energy of the two osmium-oxo π* orbitals and rendering the osmium-oxo bonding appreciably anisotropic.