Properties and Reactions of Some Inorganic and Organometallic Compounds in the Gas Phase

Author: Foster, Michael Stewart

Year: 1975

Degree: Dissertation (Ph.D.)

Advisor: Beauchamp, Jesse L.

Committee Member: Unknown, Unknown

Option: Chemistry

DOI: 10.7907/VAP4-RG14

Abstract

The gas-phase ion-molecule reactions occurring in several inorganic and organometallic systems have been examined by ion cyclotron resonance (icr) spectroscopy.

Electron attachment to sulfur hexafluoride under collision-free conditions has been shown to produce stable SF6[superscript -] by a radiative de-excitation process. Halide ion transfer reactions involving anions derived from several covalent sulfur halides produce the hydrogen dihalide anions, XHY[superscript -] (X, Y = halogen), and other interesting anionic dimers. These results have important implications for radiolysis experiments which employ SF6 as an electron scavenger.

The ion-molecule reactions of iron pentacarbonyl are characterized by the formation of polynuclear clusters containing up to four iron atoms. Extensive carbon monoxide replacement reactions are also observed with a wide variety of [sigma]- and [pi]-bonding ligands. Fe(CO)5 is shown to have a proton affinity slightly less than that of ammonia.

The fragment ions derived from ferrocene undergo charge exchange with the parent neutral and condense with it to form Fe2(C5H5)3[superscript +]. The proton affinity of ferrocene is very high, the molecule being only slightly less basic than methylamine. Some general conclusions are reached about the concept of transition metal basicity.

The proton affinity of hydrogen fluoride has been determined as 1 kcal/mole less than that of nitrogen. The anomalous behavior of HF relative to the other hydrogen halides is discussed.

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