Reaction of LaCl3 with 3 equiv of sodium metal in liquid ammonia at -78 degrees C, followed by addition of 3 equiv of HOAr (Ar=2,6-i-Pr2C6H3) in toluene produces La(OAr)(3)(NH3)(x) (1) after warming to room temperature. Dissolution of 1 in toluene followed by 6 h reflux provides La-2(OAr)(6) (2) in good yield. An X-ray crystallographic study revealed that 2 contains a dimeric unit held together with two eta(6)-arene bridges formed from aryloxide ligands with La-C(av)=3.062(10) Angstrom. The La-O distances average 2.193(5) and 2.273(5) Angstrom for terminal and bridging aryloxide ligands, respectively. Dissolution of 1 in toluene followed by vacuum filtration and crystallization from toluene without reflux yields La-2(OAr)(6)(NH3)(2)(3) in high yield. The X-ray crystal structure of 3 reveals an alternate dimeric structure bridged by oxygen atoms of the aryloxide ligands. X-ray crystallography has shown that a third compound of 1 to produce La(OAr)(3)(NH3)(4) (4) 4 displays a capped pseudo-octahedral geometry around the metal center with facial aryloxide and NH3 ligands. A fourth NH3 ligand caps the face defined by the other three. La-O distances for the aryloxide ligands average 2.252(6) Angstrom. The La-N distances for the NH3 ligands average 2.750(9) Angstrom with no significant lengthening of the capped La-N bond.