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45505-GB3
Development of Transition Metal Catalysts for Environmentally Benign Oxidation of Organic Compounds by Nitrous Oxide

Megumi Fujita, University of West Georgia

The goal of this project is to develop metal complexes that function as catalyst for environmentally friendly oxidation reactions. The research focus of this year was to find ideal metal complexation conditions for several new multidentate ligands that we had developed in the previous year (1-7) and one new ligand that we synthesized this year (8).

With ligands 1, 2 and 3, the metal complexation stage turned out to be a challenge. We have been trying many combinations of variables for the reaction conditions: metal sources, solvents, bases, supporting reagents for dehalogenation, order of addition, and purification process. The variables for ligands 1, 2 and 3 are summarized in the following scheme.

After each reaction, the putative product was examined by 1H NMR. In most cases we saw a mixture of multiple species. In some cases the product could not be observed by the NMR technique: they were probably paramagnetic. So far, the conditions that gave relatively clean product (major single product plus some minor byproducts) was the use of LDA as a base and then mixing it with NiBr2 pre-treated with AgOTf. We are currently refining this approach, adjusting the reaction time, temperature, solvent, and workup procedures. We will also test a no-base conditions (direct complexation between the protonated ligand and metal halide, upon heating).

The crystallization attempts of some relatively clean products, using non-coordinating solvents, have apparently resulted in irreversible formation of less soluble species: probably aggregate of complexes as a result of bridging of halides over multiple metal centers. We are currently exploring crystallization conditions always in the presence of a coordinating solvent.

Ligands 4, 5, 6 and 7 all reacted with early transition metal sources (TiCl4 and VOCl3) and the formation of a new, clean product was confirmed 1H NMR. However, our efforts to crystallize the products so far have been unsuccessful. We plan to further explore different crystallization conditions. An interesting observation was that while the tridentate ligands 5 and 7 did not react with Fe(OTf)2(NCCH3)2, the analogous tetradentate ligands 4 and 6 did. The latter, however, showed a mixture of two species. The reaction conditions should be refined to obtain a single product.

Ligand 8, which we newly synthesized this year, showed similar reactivity to that of the non-linear analog 6. We recently found that MoO2(acac)2, pre-treated with 2 equivalents of TfOH, gives a clean product with ligand 8. VOCl3 was another promising metal source if it was post-treated with AgOTf. These two reactions are currently repeated in a larger scale so the products can be fully characterized.

Future work will involve the full characterization of the metal complexes and testing them as catalysts for oxidation of hydrocarbons by environmentally benign oxidants such as N2O and H2O2. Other O-atom transfer agents such as peroxides, iodosobenzene and hypochlorites will be studied as well.

The grant paid for chemicals, supplies, and elemental analysis. Four undergraduate students were actively engaged in this research throughout the year. Two of them continued in the summer of 2008 and the grant financially supported them as well as the PI. The tentative results of this project were presented in three reginal/national meetings: the Southeastern Regional Meeting of the American Chemical Society 2007 (Greenville, SC, October 24-27, 2007), American Chemical Society National Meeting (New Orleans, 6-10 April 2008), and at the National Conference on Undergraduate Research (Salisbury, MD, April 10-12, 2008).

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