Thesis (Ph.D.)--McMaster University, 2005. / Supervisor: John Fitzmaurice Valliant. Includes bibliographical references. Also available online.

Thesis (Ph. D.)--University of Washington, 1997. / Vita. Includes bibliographical references (leaves [158]-172).

This Thesis extends the chemistry of group VII transition metal oxide fluorides, namely ReO3F and MnO3F. The fundamental chemistry of ReO3F has been significantly extended with the development of its high-yield and high-purity synthesis. This has been achieved by solvolysis of Re2O7 in anhydrous HF (aHF) followed by reaction of the water formed with dissolved F2 at room temperature. The improved synthesis has allowed the Lewis acid and fluoride-ion donor-acceptor properties of ReO3F to be further investigated. The Lewis acid-base complex, (HF)2ReO3F·HF, was obtained by dissolution of ReO3F in aHF at room temperature and was characterized by vibrational spectroscopy with aid of quantum-chemical calculations and single-crystal X-ray diffraction at −173 °C. The HF molecules are F-coordinated to rhenium, representing the only known example of an HF complex with rhenium. The study of the fluoride-ion acceptor properties of ReO3F resulted in the syntheses and characterization of the [{ReO3(μ-F)}3(μ3-O)]2−, [ReO3F3]2−, and [ReO3F2]− anions. The [{ReO3(μ-F)}3(μ3-O)]2− anion was obtained as the [N(CH3)4]+ salt by the reaction of stoichiometric amounts of ReO3F and [N(CH3)4]F in CH3CN solvent. The anion was structurally characterized in CH3CN solution by 1D and 2D 19F NMR spectroscopy and in the solid state by Raman spectroscopy and a single-crystal X-ray structure determination of [N(CH3)4]2[{ReO3(μ-F)}3(μ3-O)]·CH3CN. The structure of the [{ReO3(μ-F)}3(μ3-O)]2– anion consists of three ReO3F units linked to each other through dicoordinate bridging fluorine atoms (F) and a central tricoordinate bridging oxygen atom (O3). Calculated vibrational frequencies and Raman intensities of the [{MO3(μ-F)}3(μ3-O)]2− (C3v) and [{MO3(μ-F)}3(μ3-F)]− (C3v) anions (M = Re, Tc) have been used to assign the Raman spectrum of [N(CH3)4]2[{ReO3(μ-F)}3(μ3-O)]·CH3CN. The fac-[ReO3F3]2− and [ReO3F2]− anions have been synthesized by the reactions of ReO3F with CsF and KF in aHF, and by reaction of ReO3F with NOF. Additionally, the [ReO3F2]− anion has been synthesized by the reaction of ReO3F with [NH4]F in aHF. Both anions were characterized by Raman spectroscopy in the solid state and single-crystal X-ray diffraction. The calculated vibrational frequencies of the fac-[ReO3F3]2− (C3v) and [(µ-F)4(ReO3F)4]4− (C4v) anions were used to assign the Raman spectra of fac-[ReO3F3]2− and [ReO3F2]−, respectively. The rhenium atoms in the open-chain, fluorine-bridged [ReO3F2]− anion and the monomeric fac-[ReO3F3]2− anion are six-coordinate with a facial arrangement of the oxygen ligands. The fluoride-ion donor properties were established by the reactions of ReO3F with excess AsF5 and SbF5/SO2ClF. Both reactions resulted in the formation of white friable solids, µ-O(ReO2F)(AsF5)∙2AsF5 and [ReO3][Sb3F16]. The [ReO3][Sb3F16] salt is stable at room temperature and decomposes to [ReO2F2][SbF5], when maintained at 45 oC under dynamic vacuum. The µ-O(ReO2F)(AsF5)∙2AsF5, however, slowly decomposes at 0 oC to ReO3F and AsF5. Both products were characterized by Raman spectroscopy in the solid state with aid of quantum-chemical calculations. The vibrational analyses revealed that the geometry of [ReO3][Sb3F16] is consistent with a trigonal pyramidal arrangement of oxygen atoms around rhenium, whereas in µ-O(ReO2F)(AsF5)∙2AsF5, ReO3F interacts with one of the AsF5 molecules through an O-bridge, which represents the first example of such type of bonding. The reactions of µ-O(ReO2F)(AsF5)∙2AsF5 and [ReO3][Sb3F16] with CH3CN resulted in the formation of the white salts, [O3Re(NCCH3)3][PnF6] (Pn = As, Sb), which were characterized by Raman spectroscopy. The reactivity of ReO3F has been extended to the synthesis of a new Re(VII) oxide fluoride, (μ-F)4{[μ-O(ReO2F)2](ReO2F2)2}, which was synthesized by the reaction of 1:3 molar ratio of ReO3F and ReO2F3. The compound, (μ-F)4{[μ-O(ReO2F)2](ReO2F2)2}, a rare example of an O-bridged rhenium oxide fluoride, has been characterized by single-crystal X-ray diffraction and solid-state Raman spectroscopy. The vibrational assignments of (μ-F)4{[μ-O(ReO2F)2](ReO2F2)2} were confirmed by 18O-enrichment and quantum-chemical calculations. The improved synthesis of ReO3F has also led to the synthesis and characterization of the novel [XeOXeOXe]2+ cation as its [μ-F(ReO2F3)2]− salt by the low-temperature reaction of ReO3F and XeF2 in aHF. The [XeOXeOXe]2+ cation provides an unprecedented example of a xenon(II) oxide and a noble-gas oxocation as well as a rare example of a noble-gas dication. The crystal structure of [XeOXeOXe][µ-F(ReO2F3)2]2 consists of a planar, zigzag-shaped [XeOXeOXe]2+ cation (C2h symmetry) that is fluorine bridged through its terminal xenon atoms to two [µ-F(ReO2F3)2]– anions. The Raman spectra of the natural abundance and 18O-enriched [XeOXeOXe]2+ salts are consistent with a centrosymmetric (C2h) cation geometry. Quantum-chemical calculations were used to aid in the vibrational assignments of [Xe16/18OXe16/18OXe][µ-F(Re16/18O2F3)2]2 and to assess the bonding in [XeOXeOXe]2+ by NBO, QTAIM, ELF, and MEPS analyses. Ion pair interactions occur through Re–Fμ---Xe bridges, which are predominantly electrostatic in nature and result from polarization of the Fμ-atom electron densities by the exposed core charges of the terminal xenon atoms. Each xenon(II) atom is surrounded by a torus of xenon valence electron density comprised of the three valence electron lone pairs. The positive regions of the terminal xenon atoms and associated fluorine bridge bonds correspond to the positive σ-holes and donor interactions that are associated with “halogen bonding”. The reactions of MnO3F with noble-gas fluorides, KrF2 and XeF6, have been studied as the possible synthetic routes to MnOF5 and MnO2F3. The reaction of MnO3F with KrF2 yielded a red solid, which was isolated as a crystalline solid at room temperature and its crystal structure was assigned to manganese(V) fluoride, MnF5. The crystal structure of polymeric MnF5 consists of MnF6-octahedra which are trans-coordinated through fluorine bridges. The geometrical parameters of MnF5 could not be reliably determined due to unresolved twinning issues. The reaction of MnO3F with KrF2 in the presence of K[HF2] yielded a red-orange solid mixture of K[MnF6] (soluble in HF) and MnF3 (insoluble in HF). The HF solution of the solid mixture was characterized by 19F NMR spectroscopy and the resonance observed in the 19F NMR spectrum was preliminary assigned to [MnF6] by comparison with the chemical shift observed in the 19F NMR spectrum of MnO3F. Additionally, MnO3F was characterized by 19F−55Mn COSY NMR and 55Mn NMR spectroscopies, the latter provided the first 1J(19F−55Mn) coupling constant. The K[MnF6] salt was also characterized by single-crystal X-ray diffraction. The resulting octahedral geometry is imposed by symmetry, therefore, the anticipated Jahn-Teller distortion, which would result in D4h symmetry for the [MnF6] anion, could not be observed. The reaction of MnO3F with XeF6 resulted in the isolation of [Xe2F11]2[MnF6] and [XeF5]2[MnF6]. Both salts were characterized by low-temperature single-crystal X-ray diffraction. The [Xe2F11]2[MnF6] salt was additionally characterized by low-temperature Raman spectroscopy with the aid of quantum-chemical calculations, whereas the assignment of the known Raman spectrum of [XeF5]2[MnF6] has been improved in the present work. / Thesis / Doctor of Philosophy (PhD)

Call number: LD2668 .T4 1964 H67 / Master of Science

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

This thesis describes the synthesis, characterisation and reactivity of new manganese and rhenium(I) NHC complexes, which have been investigated both thermally and photochemically and the results contrasted with existing phosphine analogues in the literature. Cp’Mn(CO)2(NHC) (NHC = IEt2Me2 1, IMes 2, IiPr2Me2 3 and IPr 4) were synthesised and investigated by TRIR spectroscopy. Loss of CO was observed after 355 nm irradiation to form agostically stabilised intermediates, which reformed the parent species by recombination with CO on the nanosecond timescale. Loss of NHC was not observed, in contrast to Cp’Mn(CO)2(PPh3) which lost both CO and PPh3 upon photolysis. [Re(NHC)(Bpy)(CO)3]BAr4F (NHC = IEt2Me2 5, IMes 6) were synthesised and investigated by TRIR spectroscopy and UV/Vis absorption and emission spectrometry. Inclusion of an NHC altered the excited state manifold of the complexes, favouring population of the 3MLCT over the 3IL excited state. The lowest energy excited state for both 5 and 6 proved to be a 3MLCT excited state at 298 and 77 K. In contrast, [Re(PPh3)(Bpy)(CO)3]BAr4F exhibited 3MLCT at 298 K, but 3IL at 77 K. A series of complexes, M(NHC)(CO)4X and M(NHC)2(CO)3X (M = Re, X = Cl; M = Mn, X = Br) formed upon reaction of the corresponding M(CO)5X species and free NHC. The substitution pattern was dictated by the steric bulk of the NHC. Generation of the corresponding cations by halide abstraction was investigated. M(NHC)2(CO)3X was found to form agostic stabilised species upon halide abstraction by NaBAr4F in CH2Cl2. Under the same conditions, Re(IPr)(CO)4Cl was found to form the dichloromethane complex, [Re(IPr)(CO)4(η1-CH2Cl2)]BAr4F. In C6H5F solution under an atmosphere of dihydrogen, the CH2Cl2 ligand could be displaced by H2 to form the dihydrogen species, [Re(IPr)(CO)4(H2)]BAr4F.

Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1979. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Vita. / Includes bibliographical references. / Ph.D.