The reactions of Ln(hfacac)(3) with the bdmapH ligand and Cu(OCH3)(2) or CU2(O2CCH3)(4)(H2O)(2) have been investigated where hfacac = hexafluoroacetylacetonato, bdmapH = 1,3-bis(dimethylamino)-2-propanol. The hfacac ligand in these reactions has been found to undergo decomposition or cycloaddition with 1,1,1-trifluoro-2,2-propanediol. Two dinuclear compounds, Ln(2)(hfacac)(4)(bdmap)(2)(H2O)(2)(THF)(2), (1, Ln = Pr) and LnCu(bdmapH)(2)-(hfacac)(2)(O2CCF3)L (Ln = Pr, 2a; Y, 2b; L = 2-methyl-2,4,6-tris(trifluoromethyl)-1,3-dioxane-4,6-diolato) have been isolated from the reaction of Ln(hfacac)(3) with Cu(OCH3)(2) and bdmapH in a 1:1:2 ratio in THF. These two compounds also were obtained by independent syntheses. A trinuclear compound, LnCu(2)(hfacac)(bdmap)(3)(O-2-CCH3)(2)(O2CCF3)(hfacacH) (Ln = Nd, 3a; Pr, 3b), was obtained from the reaction of Ln(hfacac)(3) with Cu-2(O-2-CCH3)(4)(H2O)(2) and bdmapH in a 1:1:3 ratio in THF. The crystal structures of these compounds have been determined by X-ray diffraction analyses. Their thermal behavior has been examined by themogravimetric analysis. The magnetic properties of compounds 1, 2b, and 3b were examined by EPR and magnetic susceptibility measurements. Crystal data : 1, triclinic, P ($) over bar 1, a = 12.00(1) Angstrom, b = 13.71(1) Angstrom, c = 11.284(7) Angstrom, alpha = 112.59(6)degrees, beta = 107.06(7)degrees, gamma = 97.48(8)degrees, V = 1575(3) Angstrom(3), d(calc) = 1.57 g cm(-3), Z = 1; 2a, monoclinic, Cc, a = 18.205(5) Angstrom, b = 18.350(6) Angstrom, c = 15.924(4) Angstrom, beta = 94.96(2)degrees, V = 5299(2) Angstrom(3), d(calc) = 1.72 g cm(-3), Z = 4; 3a, monoclinic, P2(1)/n, a = 12.027(4) Angstrom, b = 15.222(4) Angstrom, c = 32.07(2) Angstrom, beta = 100.13(4)degrees, V = 5894(5) Angstrom(3), d(calc) = 1.61 g cm(-3), Z = 4.