Document Type

Dissertation

Degree

Doctor of Philosophy

Major

Chemistry, Organic

Date of Defense

5-17-2013

Graduate Advisor

Eike Bauer, PhD

Committee

Kristin Carbone-Lopez

Christopher Spilling

Keith Stine

Abstract

Several new η5-indenyl (Ind) complexes of iron featuring phosphinooxazoline (PHOX) ligands were synthesized and spectroscopically characterized and in a few cases structurally. The complexes were synthesized using phosphinooxazoline ligands and the corresponding iron precursor [Fe(η5-Ind) I(CO)2], yielding novel piano-stool iron complexes of the general formula [Fe(η5-Ind)(CO)(PHOX)]+ in 73% to 81% isolated yields. The complexes were tested for their efficacy in a carbon-carbon bond formation known as the Mukaiyama aldol reaction. The [Fe(η5-Ind)(CO)(PHOX)]+ complexes were capable of activating the carbonyl of aromatic aldehydes towards by attack 1-(tertbutyldimethylsilyloxy)-1-methoxyethene to form the expected silyl protected β-hydroxyesters. In these complexes, the η5-η3 haptotropic shift of the indenyl ligand, have shown to undergo this shift 100 times faster than their cyclopentadienyl (Cp) analogues. Accordingly, a noticeable increase in catalytic activity was observed in the Mukaiyama aldol reaction upon exchange of the Cp ligand for the Ind ligand

Included in

Chemistry Commons

Share

COinS