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Properties and reactions of some inorganic and organometallic compounds in the gas phase

Citation

Foster, Michael Stewart (1975) Properties and reactions of some inorganic and organometallic compounds in the gas phase. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-09202007-080247

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.

Item Type:Thesis (Dissertation (Ph.D.))
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Beauchamp, Jesse L.
Thesis Committee:
  • Unknown, Unknown
Defense Date:4 October 1974
Record Number:CaltechETD:etd-09202007-080247
Persistent URL:http://resolver.caltech.edu/CaltechETD:etd-09202007-080247
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:3664
Collection:CaltechTHESIS
Deposited By: Imported from ETD-db
Deposited On:20 Sep 2007
Last Modified:26 Dec 2012 03:01

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