Gerken, Michael

Permanent URI for this collection

https://opus.uleth.ca/handle/10133/5926

Browse

Browsing Gerken, Michael by Subject "Cations"

Now showing 1 - 3 of 3
  • Thumbnail Image
    Item
    Interactions between SF4 and fluoride: a crystallographic study of solvolysis products of SF4·nitrogen-base adducts by HF
    (American Chemical Society, 2016) Goettel, James T.; Kostiuk, Nathan; Gerken, Michael
    Adducts between SF4 and a nitrogen base are easily solvolyzed by HF, yielding the protonated nitrogen base and fluoride. Salts resulting from the solvolysis of SF4·NC5H5, SF4·NC5H4(CH3), SF4·NC5H3(CH3)2, and SF4·NC5H4N(CH3)2 have been studied by Raman spectroscopy and X-ray crystallography. Crystal structures were obtained for pyridinium salts [HNC5H5+]F–·SF4 and [HNC5H5+]F–[HF]·2SF4, the 4-methylpyridinium salt [HNC5H4(CH3)+]F–·SF4, the 2,6-methylpyridinium salt [HNC5H3(CH3)2+]2[SF5–]F–·SF4, and 4-(dimethylamino)pyridinium salts [HNC5H4N(CH3)2+]2[SF5–]F–·CH2Cl2 and [NC5H4N(CH3)2+][HF2–]·2SF4. In addition, the structure of [HNC5H4(CH3)+][HF2–] was obtained. 4,4′-Bipyridyl reacts with SF4 and 1 and 2 equiv of HF to give the 4,4′-bipyridinium salts [NH4C5–C5H4NH+]F–·2SF4 and [HNH4C5–C5H4NH2+]2F–·4SF4, respectively. These structures exhibit a surprising range of bonding modalities and provide an extensive view of SF4 and its contacts with Lewis basic groups in the solid state. The interactions range from the strong F4S–F– bond in the previously observed SF5– anion to weak F4S---F–, F4S(---F–)2, and F4S(---FHF–)2 dative bonds.
  • Thumbnail Image
    Item
    Solid-state structure of a protonated ketones and aldehydes
    (Wiley, 2017) Stuart, Daniel; Wetmore, Stacey D.; Gerken, Michael
    Protonated carbonyl compounds have been invoked as intermediates in many acid-catalyzed organic reactions. To gain key structural and electronic data about such intermediates, oxonium salts derived from five representative examples of ketones and aldehydes are synthesized in the solid state, and characterized by X-ray crystallography and Raman spectroscopy for the first time. DFT calculations were carried out on the cations in the gas phase. Whereas an equimolar reaction of the carbonyl compounds, acetone, cyclopentanone, adamantanone, and acetaldehyde, with SbF5 in anhydrous HF yielded mononuclear oxonium cations, the same stoichiometry in a reaction with benzaldehyde resulted in formation of a hemiprotonated, hydrogen-bridged dimeric cation. Hemiprotonated acetaldehyde was obtained when a 2:1 ratio of aldehyde and SbF5 was used. Experimental and NBO analyses quantify the significant increase in electrophilicity of the oxonium cations compared to that of the parent ketones/aldehydes.
  • Thumbnail Image
    Item
    Stabilization of [WF5]+ by bidentate N-donor ligands
    (Wiley, 2019) Turnbull, Douglas; Wetmore, Stacey D.; Gerken, Michael
    Transition-metal hexafluorides do not exhibit fluoride-ion donor properties in the absence of donor ligands. We report the first synthesis of donor-stabilized [MF5]+ derived from a transition-metal hexafluoride via fluoride-ion abstraction using WF6(L) (L=2,2′-bipy, 1,10-phen) and SbF5(OSO) in SO2. The [WF5(L)][Sb2F11] salts and [WF5(1,10-phen)][SbF6]⋅SO2 have been characterized by X-ray crystallography, Raman spectroscopy, and multinuclear NMR spectroscopy. The reaction of WF6(2,2′-bipy) with an equimolar amount of SbF5(OSO) reveals an equilibrium between [WF5(2,2′-bipy)]+ and the [WF4(2,2′-bipy)2]2+ dication, as determined by 19F NMR spectroscopy. The geometries of the cations in the solid state are reproduced by gas-phase geometry optimizations (DFT-B3LYP), and NBO analyses reveal that the positive charges of the cations are stabilized primarily by compensatory σ-electron donation from the N-donor ligands.