Reactions of Manganese Carbonyl Radicals: Electron Transfer, Atom Transfer and Substitution

The photochemical reaction of Mn(,2)(CO)(,10) with pyridine and several alkyl- and halogen-substituted pyridines as neat solvents has been studied. Initial products of the reaction are Mn(,2)(CO)(,9)py and {Mn(CO)(,3)(py)(,3)('+)}{Mn(CO)(,5)('-)}. Continued photolysis leads eventually to {Mn(py)(,6)('+2)}{Mn(CO)(,5)('-)}(,2) as the final product. The rate of conversion of Mn(,2)(CO)(,10) and molar ratio of the final products is dependent upon the pyridine solvent. The results support a radical pathway involving electron transfer from Mn(CO)(,5-n)py(,n) to Mn(,2)(CO)(,10).(,)

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

• Mccullen, Sharon Brawner

• Chemistry, Inorganic

Identifier

(UMI)AAI8209607

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70185