Various synthetic routes to Cu(II) and Ba fluorocarboylate derivatives as possible metal organic deposition (MOD) precursors of high Tc superconductors have been explored. The reactions between [Cu 2 (TFA) 4 ] ∞ or Cu 2 (TFA) 4 (MeOH) 2 and [Ba(TFA) 2 ] m (TFA=CF 3 CO 2 ) with various O- and N-donor ligands give adducts such as Cu 2 (TFA) 4 L 2 (L=THF, OHC 2 H 4 O i Pr), Cu(TFA) 2 (pmdeta) (pmdeta=N,N,N′,N″,N″-pentamethyldiethylenetriamine) and Ba(TFA) 2 (mdeaH 2 ) 3 or Ba(TFA) 2 (teaH 3 ) 2 (mdeaH 2 =N-methyldiethanolamine, teaH 3 =triethanolamine). The TFA ligands on copper(II) are quite labile, giving the tetranuclear [Cu(μ,η 2 -TFA)(μ 3 ,η 2 -OC 2 H 4 NMe 2 )] 4 ·0.25THF carboxylatoalkoxide by reacting Cu 2 (TFA) 4 (MeOH) 2 with dimethylaminoethanol. In contrast to the Cu–TFA derivatives, the perfluorobutyrate Cu 2 (PFB) 4 (THF) 2 (PFB=O 2 CC 3 F 7 ) is volatile and sublimes at 190°C/2×10 −4 Torr. Difluoroacetate derivatives Cu 2 (O 2 CCHF 2 ) 4 (THF) 2 and [Ba(O 2 CCHF 2 ) 2 ] m have also been prepared. In addition to elemental analysis, FT-IR, 1 H NMR or ESR spectroscopies, some adducts have also been characterized by single crystal X-ray diffraction. Cu 2 (μ,η 2 -PFB) 4 (THF) 2 and Cu 2 (μ,η 2 -TFA) 4 (η 1 -OHC 2 H 4 O i Pr) 2 show the usual paddle-wheel structure of the dinuclear Cu(II) carboxylate adducts. The barium derivative with N-methyldiethanolamine is the first example of an ionic barium trifluoroacetate derivative, all trifluoroacetates acting as counter ion.