The Doerrer group has prepared several families of homoleptic fluorinated aryloxide and alkoxide complexes of first-row transition metals.  Due the increased Bronsted acidity of the fluorinated alcohols, and the concomitant reduced basicity of the alkoxides, these complexes are characterized by three distinct features: (1) reduced bridging of these ligands between metals in their complexes (2) reduced water sensitivity of these complexes and (3) medium strength ligand fields which can engender unusual oxidation states.  This talk will include discussion of the extension of this chemistry into water with the earlier transition metals V and Mn, including comparison to some Cr compounds previously prepared by J. K. Kochi.  Mono, di-, and hexanuclear species will be discussed.  The mononuclear complexes are often five-coordinate and have the anionic form [M(pinF2)(OH)x]n- in which OHx is a ligand derived from water with two, one, or zero protons.  Dinuclear species with one (pinF) ligand per metal center and other bridging ligands have been observed.  The syntheses and spectroscopic characterization will be reported, as well as the complexes’ three-dimensional and electronic structures will be discussed and their reactivity as a function of pH and oxidizing environment.

Terminal oxo, hydroxo, and water ligands in 3d perfluoropinacolate complexes

256th National Meeting (2018)

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