Lewis acid properties of the XeF[sup +] cation and its adducts with organic nitrogen bases

Thesis/Dissertation · Tue Jan 01 04:00:00 EST 1991

OSTI ID:7283761

Emara, A A.A.

This Thesis describes the synthesis and spectroscopic characterization of noble-gas compounds containing Xe-N bonds in solution by multinuclear magnetic resonance (multi-NMR) spectroscopy and in the solid state by low-temperature Raman spectroscopy. This work represents an extension of noble-gas chemistry and the synthesis of novel xenon-nitrogen bonded compounds. The key synthetic approach involves the interaction of the Lewis acid XeF[sup +] with an organic nitrogen Lewis base, where the organic nitrogen base must be resistant to oxidation by the XeF[sup +] cation. Hydrogen cyanide, alkyl nitriles, perfluorophenyl nitrile and perfluoropyridine derivatives were investigated as potential ligands for xenon (II). The electron pairs of nitriles and perfluoropyridines have been shown to interact with the Lewis acid XeF[sup +] resulting in the cations RC[triple bond]N-XeF[sup +] (R = H, CH[sup 3], CH[sub 2]F, CH[sub 2]Cl, C[sub 2]H[sub 5], CH[sub 2]FCH[sub 2], n-C[sub 3]H[sub 7], CH[sub 2]FCH[sub 2]CH[sub 2], CH[sub 3]CHFCH[sub 2]CHF[sub 2]CH[sub 2]CH[sub 2]CH[sub 3]CF[sub 2]CH[sub 2], n-C[sub 4]H[sub 9], CH[sub 3]CHFCH[sub 2]CH[sub 2], (CH[sub 3])[sub 2]CH, (CH[sub 3])[sub 3]C, FCH[sub 2]C (CH[sub 3])H, ClCH[sub 2]C(CH[sub 3])H and C[sub 6]F[sub 5]) and R[sub F]C[sub 5]F[sub 4]N-XeF[sup +] (R[sub F] = F, 2-CF[sub 3], 3-CF[sub 3], 4-CF[sub 3]). These cations have been characterized in HF and/or BrF[sub 5] by [sup 129]Xe, [sup 19]F, [sup 15]N, [sup 14]N, [sup 13]C and [sup 1]H NMR spectroscopy and in the solid state by low-temperature Raman spectroscopy. The thermal stabilities of RC[triple bond]N-XeF[sup +]AsF[sub 6][sup [minus]] salts have been examined. The solvolytic behaviors of the adduct salts, RC[triple bond]N-XeF[sup +]AsF[sub 6][sup [minus]], have been studied in anhydrous HF solvent. The decompositions of the nitrile adduct cations CH[sub 3](CH[sub 2])[sub n]C[triple bond]N-XeF[sup +] (n = 0-3) have been monitored in HF solution by multi-NMR spectroscopy.

• Research Organization: McMaster Univ., Hamilton, ON (Canada)
• OSTI ID: 7283761
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
664200 -- Spectra of Atoms & Molecules & their Interactions with Photons-- (1992-)
74 ATOMIC AND MOLECULAR PHYSICS
ADDUCTS
CHEMICAL PROPERTIES
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HYDROGEN COMPOUNDS
INORGANIC ACIDS
LEWIS ACIDS
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
RAMAN SPECTRA
RARE GAS COMPOUNDS
RESONANCE
SPECTRA
XENON COMPOUNDS
XENON FLUORIDES