The Photochemical Reactions of Dirhenium Decacarbonyl With Water and of Dinuclear Rhenium Carbonyl Complexes Substituted by Nitrogen Bases

The photochemistry of Re(,2)(CO)(,10) with H(,2)O in THF and other solvents is examined. The final products under sunlamp irradiation are {Re(CO)(,3)OH}(,4) and H(,2) but several intermediates are also identified. Complexes which are established as crucial intermediates along the reaction pathway include HRe(CO)(,5) and eq-Re(,2)(CO)(,9)(OH(,2)). Other rhenium carbonyl hydrides are also detected but are formed through side reactions of HRe(CO)(,5). Eq-Re(,2)(CO)(,9)(OH(,2)) is produced selectively under 313 nm irradiation; quantum yield measurements at this wavelength indicate that formation of the aqua complex proceeds through dissociative substitution of H(,2)O for CO in photogenerated Re(CO)(,5)(.). The first order rate constant for CO loss from Re(CO)(,5)(.) is estimated to be approximately 10('1) s('-1). A sequence of intermediates leading from eq-Re(,2)(CO)(,9)(OH(,2)) to {Re(CO)(,3)OH}(,4) and HRe(CO)(,5) are proposed involving cross-coupling of radical species, thermal dissociation of bound H(,2)O molecules, oxidative addition of H-OH across two metal centers, and metal carbonyl hydride elimination. Supporting thermal and photochemical reactions of Re(,2)(CO)(,10) and eq-Re(,2)(CO)(,9)(OH(,2)) are also described.

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

• Gard, David Richard

• Chemistry, Inorganic

Language dc:language

eng

Identifier

(UMI)AAI8114425

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/67261