Whitmire, Kenton H.2009-06-042009-06-042002Guzman-Jimenez, Ilse Yolanda. "Applications of chalcogen containing iron carbonyl clusters: Examination of self-assembled films and homogeneous carbonylation catalysis of methanol." (2002) Diss., Rice University. <a href="https://hdl.handle.net/1911/18086">https://hdl.handle.net/1911/18086</a>.https://hdl.handle.net/1911/18086Thin 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.67 p.application/pdfengCopyright is held by the author, unless otherwise indicated. Permission to reuse, publish, or reproduce the work beyond the bounds of fair use or other exemptions to copyright law must be obtained from the copyright holder.Inorganic chemistryApplications of chalcogen containing iron carbonyl clusters: Examination of self-assembled films and homogeneous carbonylation catalysis of methanolThesisTHESIS CHEM. 2002 GUZMAN-JIMENEZ