2004 Progress Report: Green Oxidation Catalysts for Fine Chemical Synthesis

EPA Grant Number: R829553
Title: Green Oxidation Catalysts for Fine Chemical Synthesis
Investigators: Shapley, Patricia A.
Institution: University of Illinois at Urbana-Champaign
EPA Project Officer: Carleton, James N
Project Period: January 1, 2002 through December 31, 2004
Project Period Covered by this Report: January 1, 2004 through December 31, 2005
Project Amount: $325,000
RFA: Technology for a Sustainable Environment (2001) RFA Text |  Recipients Lists
Research Category: Sustainability , Pollution Prevention/Sustainable Development


The objective of this research project is to synthesize a series of new heterometallic oxidation catalysts with a range of steric and electronic properties as a “toolbox” of catalysts. Ideally, each of these would be effective for the oxidation of only one functional group in a particular substrate. Chiral catalysts would be used for asymmetric oxidations. Molecular oxygen and hydrogen peroxide will be the only stoichiometric oxidants used. A second objective is to find methods for the chemical transformation of agricultural products, such as fatty acids from soy, to fine chemicals. We also intend to prepare water-soluble catalysts for the oxidation of carbohydrates. To reduce the quantity of volatile organic solvents used in oxidation reactions, we will test water-soluble complexes for catalytic activity in water. Some complexes will be tested in alternative solvents, such as supercritical CO2. Supported metal complexes will be tested as heterogeneous catalysts.

Progress Summary:

The fine chemical industries require more selective, robust catalysts for the oxidation of single functional groups in complex precursors with molecular oxygen. This project has focused on the development of new, green alternatives to current oxidation processes. In the past year, we have made significant progress in the synthesis of more robust, homogeneous catalysts for selective oxidation reactions. We examined the reactivity of a series of heterometallic µ-sulfido complexes in the environmentally friendly solvent, supercritical carbon dioxide, and compared the results to the reactivity of these complexes in traditional organic solvents. Although each of the complexes (dppe)M(µ 3-S)2 {Ru(N)Me2}2 and (dppe)M(µ 3-S)2 {Os(N)(CH­ 2SiMe 3) 2} 2 (M = Pt, Pd, Ni) will catalyze the oxidation of alcohols with O2, their reactivity in the oxidation of alkenes varies with the nature of the metal. At high temperatures, the sulfido ligand reacts with O2 and sulfur oxides form. We have synthesized osmium and ruthenium precursors to new series of heterometallic µ-oxo complexes, [N(n-Bu)4][cis-M’(N)(OH) 2R2] and [M’(N)(OH)R2]2 (M’=Ru, Os). These complexes react with a wide variety of trimethylsiloxy complexes M”(OSiMe3)2L x to form new complexes that are potentially more robust oxidation catalysts. Many of our new catalysts can be supported on silica and retain the selectivity of the homogeneous catalysts. We have prepared chiral-at-metal complexes that are stereochemically rigid for use in asymmetric oxidation systems. Finally, we have demonstrated that selective C-H oxidation in saturated fatty acids can be catalyzed by picolinate complexes of iron(III).

Future Activities:

The investigator did not report any future activities.

Journal Articles on this Report : 2 Displayed | Download in RIS Format

Other project views: All 16 publications 7 publications in selected types All 4 journal articles
Type Citation Project Document Sources
Journal Article Kuiper JL, Shapley PA, Rayner CM. Synthesis, structure, and reactivity of the ruthenium(VI)-Nickel(II) complex (dppe)Ni(ยต3-S)2 {Ru(N)Me2}2. Organometallics 2004;23(16):3814-3818. R829553 (2004)
R829553 (Final)
  • Abstract: ACS Publications - abstract
  • Journal Article Pool DH, Shapley PA. Chiral-at-metal osmium(VI) phosphine complexes. Organometallics 2004;23(10):2326-2335. R829553 (2004)
    R829553 (Final)
  • Abstract: ACS Publications - abstract
  • Supplemental Keywords:

    green chemistry, chemicals, water-soluble catalysts, heterometallic oxidation catalysts, oxidants, oxidation, renewable, pollution prevention, waste reduction, environmental chemistry,, RFA, Scientific Discipline, Sustainable Industry/Business, Chemical Engineering, cleaner production/pollution prevention, Environmental Chemistry, Sustainable Environment, Technology for Sustainable Environment, New/Innovative technologies, Chemistry and Materials Science, renewable feedstocks, supercritical carbon dioxide (SCCO2) technology, oxidation reactions, waste reduction, oxidation, fine chemicals, "toolbox" of catalyst, catalysts, supercritical carbon dioxide, catalytic transformations, agricultural industry, chemcial synthesis, carbon dioxide, solvent substitute, solvent replacements, pollution prevention, Volatile Organic Compounds (VOCs), chemical transformation, environmentally-friendly chemical synthesis, green chemistry, pharmaceutical industry, renewable resource, solvents, chemical synthesis

    Progress and Final Reports:

    Original Abstract
  • 2002 Progress Report
  • 2003
  • Final Report