Date of Award


Degree Type


Degree Name

Doctor of Philosophy


This thesis discusses the coordination chemistry of the fluorinated gem-diol, (CF{dollar}\sb3)\sb2{dollar}C(OH){dollar}\sb2{dollar}, "hexafluoroacetone hydrate" (HFAH). Due to the electron-withdrawing ability of the CF{dollar}\sb3{dollar} groups, the protons of this diol are acidic. Reactions of the diol with metal chlorides and alkali metal hydroxides were found to give fluorinated alkoxide complexes in which HFAH adopted four distinct coordination modes. The nature of the metal, and the amount and steric requirements of the coligand, if any, used, were identified as major factors in determining which coordination mode was adopted. The four observed modes are (i) as a chelating dialkoxide, {dollar}\rm\sp-OC(CF\sb3)\sb2O\sp-{dollar}, (ii) as a dimerized, chelating dialkoxide, {dollar}\rm\sp-OC(CF\sb3)\sb2OC(CF\sb3)\sb2O\sp-{dollar}, (iii) as a bridging dialkoxide, and (iv) as the monodentate, monovalent ion {dollar}\rm\sp-OC(CF\sb3)\sb2{dollar}OH.;Crystallographic determinations of the structures of five of the products of this study were undertaken to investigate the geometries of the alkoxide ligands. Products incorporating HFAH in three of the coordination modes mentioned, (i), (ii), and (iv), were structurally characterized.;The use of HFAH illustrated the versatility of the diol as a source of fluorinated alkoxide ligands. Complexes of Cu(II), Ni(II), Co(III), Mn(II), Pt(II), Sn(II) and Sb(III) were prepared.



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