Dissertation Information for Travis M. AndersonNAME:
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SCHOOL: ADVISORS: COMMITTEE MEMBERS: MPACT Status: Fully Complete Title: Metallation and isomerization effects of polyoxometalates on catalytic oxidation reactions Abstract: In our attempts to synthesize new iron-containing Wells-Dawson polyoxometalates (POMs) for catalytic oxidation reactions, five new sandwich-type complexes have been prepared: ƒ¿ƒ¿ƒ¿ƒ¿-(NaOH 2 ) 2 Fe III 2 (P 2 W 15 O 56 ) 2 16- , ƒ¿ƒ¿ƒÀƒ¿-Cu II (OH 2 )Fe III 2 (P 2 W 15 O 56 )(P 2 (Cu II (OH 2 )) 2 W 13 O 52 ) 16- , ƒ¿ƒ¿ƒÀƒ¿-Co II (OH 2 )Fe III 2- (P 2 W 15 O 56 )(P 2 (Co II (OH 2 )) 2 W 13 O 52 ) 16- , ƒ¿ƒ¿ƒÀƒ¿-(Fe III OH 2 )(NaOH 2 )Fe III 2- (P 2 W 15 O 56 ) 2 14- , and ƒ¿ƒÀƒÀƒ¿-(Ni II OH 2 ) 2 Fe III 2 (P 2 W 15 O 56 ) 2 14- . These complexes were characterized by X-ray crystallography, 31 P NMR, IR, and elemental analysis. The complexes have been converted to tetra- n -butylammonium salts by a metathesis reaction and were used for the oxidation of alkenes by H 2 O 2 . ƒ¿ƒ¿ƒ¿ƒ¿-(NaOH 2 ) 2 Fe III 2 (P 2 W 15 O 56 ) 2 16- and ƒ¿ƒÀƒÀƒ¿-(Ni II OH 2 ) 2 Fe III 2 (P 2 W 15 O 56 ) 2 14- were the most effective catalysts, each giving more than 200 turnovers of epoxide (for the oxidation of cyclooctene) over a 40 hour period with more than 98% selectivity. |
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