Thin films have been prepared via the solution-phase-self-assembly of organometallic chalcogen-containing cluster compounds onto the surface of gold and characterized. The following anionic complexes were used as thin films precursors: [Fe3(CO)9E]2- and [HFe3(CO)9E]-, where E = S, Se, Te. The films were generated by adsorption from organic solvents (e.g., methanol, acetonitrile, acetone, and dichloromethane) onto evaporated gold and were characterized by ellipsometry, polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS), X-ray diffraction (XRD), atomic force microscopy (AFM), quartz crystal microbalance (QCM), and X-ray photoelectron spectroscopy (XPS).
[Et4N]2[Fe3(CO)9E] catalyzes the carbonylation of methanol to form methyl formate under moderate CO pressures (600--1200 psi) between 50 and 90°C. A detailed kinetic analysis of this system is reported. [Fe3(CO)9E]- selectively carbonylates methanol to methyl formate in a homogeneus reaction which first order dependent in cluster concentration, quasi second order dependent in pressure of CO. The reaction appears to be almost independent of the [OCH 3-]total at values of [OCH3 -]total ≤ 3 x 10-3 M, but at higher concentrations it appears to be first order dependence in [OCH3-]total. This system affords the opportunity to compare the effects of different main group heteroatoms in a homogeneous series.
| Identifer | oai:union.ndltd.org:RICE/oai:scholarship.rice.edu:1911/18086 |
| Date | January 2002 |
| Creators | Guzman-Jimenez, Ilse Yolanda |
| Contributors | Whitmire, Kenton H. |
| Source Sets | Rice University |
| Language | English |
| Detected Language | English |
| Type | Thesis, Text |
| Format | 67 p., application/pdf |
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