Evidence for Redox Mechanisms in Organometallic Chemisorption and Reactivity on Sulfated Metal Oxides
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Ames National Laboratory is a government-owned, contractor-operated national laboratory of the U.S. Department of Energy (DOE), operated by and located on the campus of Iowa State University in Ames, Iowa.
For more than 70 years, the Ames National Laboratory has successfully partnered with Iowa State University, and is unique among the 17 DOE laboratories in that it is physically located on the campus of a major research university. Many of the scientists and administrators at the Laboratory also hold faculty positions at the University and the Laboratory has access to both undergraduate and graduate student talent.
The Department of Chemistry seeks to provide students with a foundation in the fundamentals and application of chemical theories and processes of the lab. Thus prepared they me pursue careers as teachers, industry supervisors, or research chemists in a variety of domains (governmental, academic, etc).
History
The Department of Chemistry was founded in 1880.
Dates of Existence
1880-present
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- College of Liberal Arts and Sciences (parent college)
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Abstract
The chemical and electronic interaction of organometallic species with metal oxide support materials is of fundamental importance for the development of new classes of catalytic materials. Chemisorption of Cp*(PMe3)IrMe2 on sulfated alumina (SA) and sulfated zirconia (SZ) led to an unexpected redox mechanism for deuteration of the ancillary Cp* ligand. Evidence for this oxidative mechanism was provided by studying the analogous homogeneous reactivity of the organometallic precursors toward trityl cation ([Ph3C]+), a Lewis acid known to effect formal hydride abstraction by one electron oxidation followed by hydrogen abstraction. Organometallic deuterium incorporation was found to be correlated with surface sulfate concentration, as well as the extent of dehydration under thermal activation conditions of sulfated alumina and sulfated zirconia supports. Surface sulfate concentration dependence, in conjunction with a computational study of surface electron affinity, indicates an electron deficient pyrosulfate species as the redox active moiety. These results provide further evidence for the ability of sulfated metal oxides to participate in redox chemistry not only toward organometallic complexes, but also in the larger context of their application as catalysts for the transformation of light alkanes.