Complexes of the early lanthanides with the donor-functionalized alkoxide ligand mmp (Hmmp = HOCMe2CH2OMe, 1-methoxy-2-methylpropan-2-ol) are excellent precursors for Metal Organic Chemical Vapor Deposition (MOCVD) and Atomic Layer Deposition (ALD) of lanthanide oxides; however, their coordination chemistry, which is the subject of this paper, is rather complex. Precursors for MOCVD and ALD of lanthanide oxides are prepared by the reaction of [Ln{N(SiMe3)(2)}(3)] with 3 equiv of the alcohol Hmmp in toluene in the presence of 1 equiv of tetraglyme and are indefinitely stable in solution. Reaction of [Ln{N(SiMe3)(2)}(3)] with 3 equiv of Hmmp in the absence of stabilizing Lewis bases gives complex condensed products with empirical formula [{Ln(mmp)(3-n)}(2)O-n]. These condensed products show poor volatility and are unsatisfactory precursors for MOCVD or ALD of oxides. The cluster complex [La-3(mu(3),kappa(2)-mmp)(2)(mu(2),kappa(2)-mmp)(3)(mmp)(4)] has been prepared by careful reaction of [La{N(SiMe3)(2)}(3)] with 4 equiv of Hmmp and has been characterized by single-crystal X-ray diffraction. Salt metathesis reactions using M(mmp) (M = Li or Na) are unreliable routes to [Ln(mmp)(3)]. Crystals of the heterometallic cluster complex [NaLa3(mu(3)-OH)(mu(3),kappa(2)-mmp)(2)(mu(2),kappa(2)-mmp)(4)(mmp)(3)] were isolated from the reaction of [La(NO3)(3)(tetraglyme)] with 3 equiv of Na(mmp), and crystals of [Li(kappa(2)-Hmmp)Pr(mu(2),eta(2)-mmp)(4))LiCl] were isolated from the reaction of PrCl3 with 3 equiv of Li(mmp); both of these complexes have been characterized by single-crystal X-ray diffraction.