Mechanistic investigations of gas phase ion-molecule reactions using Fourier transform ion cyclotron resonance mass spectrometry

Miscellaneous · Fri Jan 01 00:00:00 EST 1993

OSTI ID:7273925

Van Orden, S L

Studies of the mechanisms and energetics of a variety ion-molecule reactions involving organometallic and organic ions have been performed using Fourier transform ion cyclotron resonance mass spectrometry (FTMS). The bond activation processes of V[sup +], VO[sup +], VOH[sup +], and VOCH[sub 3][sup +] with water and methanol were investigated. All ions are observed to preferentially activate the C-O bond in methanol, however C-H and O-H bond cleavage are also observed. The addition of the oxo, hydroxo, and methoxo ligands is found to significantly effect the intrinsic reactivity of the ions, relative to V[sup +]. The reactions of V(CO)[sub 5][sup [minus]] with a wide variety of molecules have revealed mechanistic details of the oxidative addition and ligand switching reactions. Studies of ligand substitution reactions support an electron transfer initiated mechanism. The chlorine atom transfer reactions of V(CO)[sub 5][sup [minus]] with chloromethanes display a correlation with C-Cl bond strength. The decomposition of metallocarboxylate anions ([M(CO)[sub x[minus]1] CO[sub 2]][sup [minus]]) was studied in an effort to understand the production of CO[sub 2] by metal carbonyl compounds, proposed as intermediates in the Water-Gas shift reaction. The reactions of PAHs with O[sup [minus][center dot]] and O[sub 2][sup [minus][center dot]] were studied to investigate the potential of isomer differentiation by chemical ionization. These reactions are characterized by a number of reactive pathways, demonstrating the ability to distinguish isomers which cannot be differentiated by other ionization techniques. Kinetic energy release measurements of the S[sub N]2 reactions of F[sup [minus]] with CH[sub 3]Cl, C[sub 6]H[sub 5]Cl, and CH[sub 3]COCl have been made using KEICR. The F[sup [minus]]/CH[sub 3]Cl reaction results in a non-statistical energy disposal.

• Research Organization: Arizona Univ., Tucson, AZ (United States)
• OSTI ID: 7273925
• Resource Relation: Other Information: Thesis (Ph.D.)
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ORGANIC COMPOUNDS
CHEMICAL REACTION KINETICS
ION CYCLOTRON RESONANCE SPECTROSCOPY
VANADIUM IONS
CHEMICAL BONDS
GASES
STRUCTURAL CHEMICAL ANALYSIS
CHARGED PARTICLES
FLUIDS
ION SPECTROSCOPY
IONS
KINETICS
REACTION KINETICS
SPECTROSCOPY
400201* - Chemical & Physicochemical Properties