(mu-Oxo)diiron complexes of [Fe((DMG)BPh(2))(2)]O-2 (1) bind one or two axial ligands within cyclophane-like cavities which lie trans to the oxo bridge. Nonbonded interactions between the bound ligand and the BPh(2) superstructure are elucidated. Hindered ligands at one site significantly reduce ligation at the remote site via peripheral contacts operating between the two superstructures surrounding the binding sites. Ligated species are characterized on the basis of visible spectra and paramagnetic shifts in the H-1 NMR spectra. The BPh(2) phenyl proton shifts were fit to a simple dipolar model. The DMG methyl, imidazole, and pyridine ligand H-1 resonances experience contact shifts which differ in magnitude and sign for the various ligated forms, LFe-O-Fe, LFe-O-FeL, and LFe-O-Fe(CH3CN). Contact shifts are consistent with spin transfer from a single unpaired electron on each low-spin iron to pi orbitals of the ligands. Restricted rotation of bound ligands within the cyclophane-like cavities is evident.