Surface Oxygen Chemistry on Some Isopoly and Heteropolyoxoanions (Polyoxoanion)

The dynamic behavior of the (alpha)-Mo(,8)O(,26)('4-), C(,6)H(,5)AsMo(,7)O(,25)('4-), and (C(,6)H(,5)As)(,2) Mo(,6)O(,24)('4-) ions as (n-C(,4)H(,9))(,4)N('+) salts in CH(,3)CN have been studied by variable temperature ('17)O NMR lineshape analysis, ('17)O spin saturation transfer techniques, and ('17)O label crossover experiments. The C(,6)H(,5)AsMo(,7)O(,25)('4-) ion shows two distinct types of fluxional behavior that can be related to the anion's structure. The low temperature process involves Mo(,6)O(,18) ring inversion accompanied by twisting of the C(,6)H(,5)AsO(,3)('2-) subunit and twisting or flipping of the MoO(,4)('2-) subunit. Only weak (>2.2(ANGSTROM)) molybdenum-oxygen bonds are broken and reformed. The higher temperature process, although mechanistically undefined, involves cleavage of stronger (1.7-2.0(ANGSTROM)) molybdenum-oxygen bonds. Evidence is presented for related processes in the (alpha)-Mo(,8)O(,26)('4-) and (C(,6)H(,5)As)(,2)Mo(,6)O(,24)('4-) ions.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2014

Author dc:creator

• Schwartz, Curtis

• Chemistry, Inorganic

Identifier

(UMI)AAI8701611

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70355