Redox Reactions of Aqueous Molybdenum(iv)

The redox chemistry of aqueous molybdenum(III), (IV), and (V) was investigated under a variety of conditions. Monomeric Mo(IV)(,aq), whether produced by the dissolution of "monomeric" Mo(IV) compounds in water or by the oxidation of Mo('3+), is unstable with respect to disproportionation. Mo(OR)(,4), (Et(,4)N)(,2)MoCl(,6), and the initial one-electron oxidation product of Mo('3+) disproportionate to give Mo('3+) and Mo(,2)O(,4)('2+), while (NH(,4))(,2)MoCl(,4)(SnCl(,3))(,2) and MoCl(,4) give Mo(,3)Cl(,12)('3-) and Mo(,2)O(,4)('2+). Mo(,3)Cl(,12)('3-) decomposes in water (t(, 1/2) = 8.3min) to produce monomeric Mo(III) chlorocomplexes in varying degrees of hydration. This instability of aqueous monomeric Mo(IV) precludes its use in the production of the stable trinuclear Mo(,3)O(,4)('4+) unit.

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

• Rahmoeller, Kenneth Mark

• Chemistry, Inorganic

Identifier

(UMI)AAI8600286

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70315