Hexafluoroacetone reacts with [(π-C5H5)Fe(CO)2]– to give (CF3)2C(OH)Fe(CO)2(π-C5H5). Hexafluoroacetylacetone (hfacH) cleaves both the carbonyl groups and the cyclopentadienyl ring from [(π-C5H5)Fe(CO)2]2 to give Fe(hfac)2. Reactions of sodium hexafluoroisopropoxide with (π-C5H5)2TiCl2, cis-(Ph3P)2PtCl2, and (Et3P)2NiCl2 give the corresponding hexafluoroisopropoxides. Sodium pentafluorophenoxide reacts more slowly with titanocene dichloride to give (π-C5H5)2Ti(OC6F5)Cl. Other related reactions are discussed.