Metathesis involving YCl 3 and sodium 1,1,1,3,3,3-hexafluoro-2-propoxide offered a mixed-metal species, YNa 3 [OCH(CF 3 ) 2 ] 6 (THF) 3 (1). The reaction between1 and yttrium and copper derivatives, β-diketonates and halides, gave access to YNa 2 [OCH(CF 3 ) 2 ] 4 (thd)(THF) 4 (2) and the Na--Cu species, Na 2 Cu[OCH(CF 3 ) 2 ] 4 (THF) 4 and [NaCu[OCH(CF 3 ) 2 ] 2 (thd)] m (5), respectively (thdH = 2,2,6,6-tetramethylheptane-3,5-dione). Alcohol interchange reactions between Y 5 O(OPr i ) 1 3 and fluoroisopropanol led to the isolation of Y[OCH(CF 3 ) 2 ] 3 L 3 [L = THF (3a) or Pr i OH (3b)] depending on the solvent, THF or hexane. The various compounds have been characterized by FT-IR, NMR ( 1 H, 1 3 C, 1 9 F) and mass spectrometry and thermogravimetric analysis. All compounds are volatile; sublimation of the Y--Na or Na--Cu species occurs with retention of the stoichiometry between the metals. The Lewis bases are readily lost during sublimation of compounds 1, 2 and 3a or 3b.