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Thesis (Ph. D.)--University of Missouri-Columbia, 1997. / Typescript. Vita. Includes bibliographical references (leaves 147-169). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 1997. / Typescript. Vita. Includes bibliographical references (leaves 147-169). Also available on the Internet.

Thesis (Ph. D.)--Auburn University, 2009. / Abstract. Includes bibliographical references.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1970. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliography.

The x-ray structures of several alkyl halide, alkyl dihalide, and hydrogen adducts to pyrazolyl-bridged diiridium complexes [special characters omitted] are determined. The diiridium (bis-pyrazolyl) core of these complexes enables contact between the two centers so that metal-metal bond formation may occur, exemplified by a short iridium-iridium distance of 2.78(I) A in the diiridium(II) complex [special characters omitted]. Oxidation mechanisms are postulated based on reaction kinetics. The oxidative addition of methyl iodide to [special characters omitted] is observed to occur by a two-step mechanism, where a high positive ΔS‡ term may be due to a highly ordered intermediate. This is proposed as evidence for an [special characters omitted] addition, where coordination of the alkyl halide is followed by halide dissociation and migration to a trans diaxial coordination site. Different kinetics of the reaction are observed in THF and benzene, which is also attributed to a polar [special characters omitted] intermediate. Occupation of the 3,3’ and 5,5’ positions of the pyrazolyl ligand decreases the reaction rate by an order of magnitude or greater, which indicates steric inhibition of the reaction by the bridging ligands. Experimental evidence for a competing light-induced reaction that corresponds to a radical-chain mechanism rather than the dark [special characters omitted] reaction is also presented. Oxidative isomerization of an iodo (iodomethylene) complex to the methylene-bridged isomer is determined to be an intramolecular process based on isotope labelling experiments and kinetics. Negligible isomerization to the bridging methylene complex under ambient conditions is attributed to coordinative saturation; the stability of [special characters omitted] is likewise due to coordinative saturation of the metal centers. The addition of hydrogen or hydride to [special characters omitted] is possible through a number of synthetic routes, but the stereochemistry of the iridium(II) hydrido complexes is such that the metal-hydride and iridium-iridium bonds do not occupy coordination sites trans to each other: it is proposed that the strong σ-trans effect of the hydride induces structural rearrangements in substitution reactions so that stereochemistry of parent complexes is not conserved. This is demonstrated by the x-ray structures of [special characters omitted]. The hydride ligand promotes nucleophilic attack on an electron-rich iridium center; thus water and other Lewis bases are found to react with the cationic diiridium hydride complex [special characters omitted]. / Graduate

The novel bimetallic hydrides [(n⁵-C₅H₅)W(N0)IH]₂ and [(n⁵-C₅H₅)W(N0)H₂]₂ can be prepared sequentially by the metathesis of [(n⁵-C₅H₅)W(N0)IH₂]₂ with Na[H₂Al(0CH₂CH₂0CH₃)₂]. Analyses of the ¹H NMR spectra of C[(n⁵-C₅H₅)W(N0)IH]₂ and [(n⁵-C₅H₅)W(N0)IH₂]₂ show the former contains hydride ligands bound to tungsten in a terminal fashion, while the latter possesses two terminal and two bridging hydrides. Addition of a Lewis base to [(n⁵-C₅H₅)W(N0)IH]₂ results in the formation of hydride species (n⁵-C₅H₅)W(N0)IHL (L = P(0Ph)₃, P(0Me)₃, PPh₃); in like manner, the dimer [(n⁵-C₅H₅)W(N0)IH₂]₂ is cleaved by triphenylphosphite to form the monomer cis or trans [(n⁵-C₅H₅)W(N0)IH₂[P(0Ph)₃]. A comparison is made of the reactivity of the tungsten-hydrogen link in the nitrosyl hydrides (n⁵-C₅H₅)- W(N0)IH[P(0Ph)₃], (n⁵-C₅H₅)W(N0)₂H, and (n⁵-C₅H₅)W(N0)IH₂[P(0Ph)₃]. The Mo(N0)₂²⁺ unit is obtained as the tetrakis-solvate via chloride abstraction from Mo(N0)₂Cl₂ by AgBF₄ or nitrosylation of Mo(C0)₆ by NOPF₆ in coordinating solvents such as nitromethane, acetonitrile, or tetrahydro-furan. The unsolvated complex [Mo(N0)₂(PF₆)₂][aub=n] is produced if the latter reaction is performed in dichloromethane; however, it readily converts to [Mo(N0)₂S₄](PF₆)₂ upon exposure to coordinating solvents (S). Hard Lewis bases (L = CH₃CN , 0PPh₃ or L₂ = 2 ,2-bipyridine replace the solvent molecules in [Mo(N0)₂S₄]X₂ (X = BF₄⁻, PF₆⁻) forming complexes [Mo(N0)₂L₄]²⁺ or [Mo(N0)₂L₂S₂]²⁺ depending upon the solvent employed. Reagents capable of being oxidized appear to reduce the dinitrosyl dication without permanent coordination to the molybdenum centre. Reduction of [Mo(NO)₂S₄](PF₆)₂ or [Mo(N0)₂(PF₆)₂][sub=b] is effected by sodium amalgam (one equivalent); addition of a ligand L₂ (L₂ = 2,2-bipyridyl, 3,4,7,8-tetramethyl-1,1O-phenanthroline) to the reaction mixture permits the isolation of [M(NO)₂L₂]₂(PF₆)₂. Addition of excess ligand results in the formation of non-nitrosyl containing species [Mp(L₂)₃]PF₆ (L = 0PPh₃ or L₂ = 3,4,7,8-tetramethyl-1 ,10-phenanthro- line). Decomposition of the nitrosyl species results from attempts to reduce [Mo(NO)₂S₄]²⁺ by two electrons. New complexes are identified by the aid of IR and ¹H, ¹⁹F, or ³¹P NMR spectroscopy and conductance measurements. Attempts to prepare thionitrosyl analogues of [Mo(N0)₂L₄]²⁺ have met with limited success; the only wel1-characterized thionitrosyls isolated in this study are the known (n⁵-C₅H₅)Cr(C0)₂NS and the new [(n⁵-C₅H₅)Mo-(N0)(NS)PPh₃]BF₄. Also discussed is the interaction of NOPF₆ with solvents. NOPF₆ has been found to react slowly with acetonitrile, a common solvent for nitro-sonium salts. / Science, Faculty of / Chemistry, Department of / Graduate

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